Imidazo-pyrimidone compounds as pesticides

ABSTRACT

The invention relates to a compound of formula (I), wherein the variables are defined in the specification. It also relates to a pesticidal mixture comprising the compound of formula (I); the use of compounds of formula (I) as an agrochemical pesticide; a method for combating or controlling invertebrate pests, a method for protecting growing plants from attack or infestation by invertebrate pests, seed comprising a compound of the formula (I); and the use of a compound of the formula (I) for protecting growing plants from attack or infestation by invertebrate pests.

The invention relates to compounds of formula (I) or an agrochemically or verterinarily acceptable salt, stereoisomer, tautomer, or N-oxide thereof

wherein the variables are as defined below. The invention also relates to the use of compounds of formula (I) as an agrochemical pesticide; to pesticidal mixtures comprising a compound of formula (I) and another pesticidal ingredient; to a method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula (I) or the pesticidal mixture; to a method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I) or the pesticidal mixture; and to seeds comprising a compound of the formula (I) or the pesticidal mixture in an amount of from 0.1 g to 10 kg per 100 kg of seeds; to a use of a compound of the formula (I) or of the pesticidal mixture for protecting growing plants from attack or infestation by invertebrate pests; and to a method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of a compound of the formula (I) or the pesticidal mixture.

Invertebrate pests and in particular insects, arachnids and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. Accordingly, there is an ongoing need for new agents for combating invertebrate pests.

WO2017/167832A1 discloses bicyclic pyrimidone compounds and their pesticidal activity. Due to the ability of target pests to develop resistance to pesticidally-active agents, there is an ongoing need to identify further compounds, which are suitable for combating invertebrate pests such as insects, arachnids and nematodes. Furthermore, there is a need for new compounds having a high pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control insects, arachnids and nematodes.

It is therefore an object of the present invention to identify and provide compounds, which exhibit a high pesticidal activity and have a broad activity spectrum against invertebrate pests.

It has been found that these objects can be achieved by substituted bicyclic compounds of formula (I), as depicted and defined below, including their stereoisomers, their salts, in particular their agriculturally or veterinarily acceptable salts, their tautomers and their N-oxides.

In a first aspect, the present invention relates to a compound of formula (I),

wherein

-   the rings A and B are fully unsaturated; -   Y is C=X, wherein X is O or S; -   E is N(R³) or C(R⁴); -   Q is N, N(R⁵) or C(R⁶); -   R¹ is H, halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,     C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkoxy, C₁-C₆-sulfenyl, C₁-C₆-sulfinyl, or     C₁-C₆-sulfonyl, which groups are unsubstituted or halogenated; -   R³, R⁵ are independently C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy,     C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, or     C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which are unsubstituted or     halogenated; C(=O)OR^(A), NR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(C),     O-C₁-C₆-alkylen-NR^(B)R^(C), C₁-C₆-alkylen-CN,     NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C), C(═O)R^(D),     C(═S)R^(D), SO₂NR^(B)R^(C), S(═O)_(m)R^(E); -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or     substituted with one or more, same or different substituents R^(F); -   R², R⁴, R⁶ are independently H, halogen, N₃, CN, NO₂, SCN, SF₅; -   C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, tri-C₁-C₆-alkylsilyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy,     C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy, C₃-C₆-cycloalkyl-C₁-C₄-alkyl,     C₃-C₆-cycloalkoxyx-C₁-C₄-alkyl, which groups are unsubstituted or     substituted with halogen, -   C(═O)OR^(A), NR^(B)R^(C), NOR^(A), ONR^(B)R^(C),     C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C),     C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C),     C(═O)R^(D), C(═S)R^(D), SO₂NR^(B)R^(C), S(═O)_(m)R^(E); -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or     substituted with one or more, same or different substituents R^(F); -   G is phenyl, or a 5- or 6-membered hetaryl; -   W is S, S(O), or S(O)₂; -   each R^(X) independently is —C(CN)R⁷R⁸, —C(R^(O))═N—N(R^(M)R^(N)),     —C(R^(O))═N—O(R^(L));     -   C₃-C₆-cycloalkyl, which is substituted with CN and which either         does not have any further substituents, or which is further         substituted with one or more, same or different substituents R⁹;         or

    -   a group of formula (I.1)

    -   

    -   wherein the ring L is a 5- or 6-membered saturated, partially or         fully unsaturated carbo- or heterocycle;

    -   wherein the ring L is a saturated, partially or fully saturated         carbo- or heterocycle, which carbo- or heterocycle is         unsubstituted or substituted with one or more, same or different         substituents R¹⁰, and wherein said heterocycle contains one or         more, same or different heteroatoms N, O, or S, and wherein said         heteroatoms N and S are oxidized or non-oxidized;

    -   wherein ring J is partially or fully unsaturated and         unsubstituted or substituted with one or more, same or different         substituents R¹¹; and

    -   wherein “&” means the connection to the remainder of the         molecule at the position of R^(X) in formula (I); -   R⁷, R⁸ are independently H, halogen, CN, C₁-C₆-alkyl,     C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy,     C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl,     C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl,     C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl; -   R⁹ CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH, C(═O)NH₂,     C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl,     C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl,     C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl,     C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl,     C₁-C₄-alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino,     di-(C₁-C₄)alkylcarbonylamino, C1-C₄-alkoxycarbonylamino, or a group     —C(R⁹¹)═NOR⁹²;     -   phenyl, which is unsubstituted or substituted with one or more,         same or different substituents selected from halogen, CN,         C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy,         C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl,         C₁-C₄haloalkylsulfonyl and C(=O)C₁-C₄-haloalkyl;     -   C₁-C₄-alkyl which is unsubstituted or substituted with one or         more, same or different substituents R⁹³;     -   R⁹¹ and R⁹² are independently H, C₁-C₄-alkyl, or         C₁-C₄-haloalkyl;     -   R⁹³ is halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl,         hydroxycarbonyl, aminocarbonyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy,         C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl,         C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl,         C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl,         C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl,         C₁-C₄alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino,         di-(C₁-C₄)alkylcarbonylamino, C₁-C₄-alkoxycarbonylamino, a group         —C(R⁹¹)═NOR⁹²;     -   each R¹⁰, R¹¹ is independently H, halogen, CN, OH;     -   C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, or         C₁-C₄-alkoxy-C₁-C₄-alkyl, which groups are unsubstituted or         halogenated; -   each R^(A) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which     groups are unsubstituted or substituted with halogen;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substitutents         R^(F); -   each R^(B) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,     C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are     unsubstituted or substituted with halogen;     -   phenyl or benzyl, which groups are unsubstituted or substituted         with one or more, same or different substituents R^(F); -   each R^(C) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,     C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are     unsubstituted or substituted with halogen;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substituents         R^(F); -   each moiety NR^(B)R^(C) may also form an N-bound, saturated 5- to     8-membered heterocycle, which in addition to the nitrogen atom may     have 1 or 2 further heteroatoms or heteroatom moieties selected from     O, S(═O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein     the N-bound heterocycle is unsubstituted or substituted with one or     more, same or different substituents selected from halogen,     C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; -   each R^(D) is independently H, CN, OH, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which     groups are unsubstituted or substituted with halogen;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substituents         R^(F); -   each R^(E) is independently C₁-C₆-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which are unsubstituted or substituted     with halogen; or     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substituents         R^(F); -   each R^(L) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which     groups are unsubstituted or substituted with one or more, same or     different substituents selected from halogen and CN;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substitutents         R^(F); -   each R^(M) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,     C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are     unsubstituted or substituted with halogen;     -   phenyl or benzyl, which groups are unsubstituted or substituted         with one or more, same or different substituents R^(F); -   each R^(N) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,     C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are     unsubstituted or substituted with halogen;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substituents         R^(F); -   each moiety NR^(M)R^(N) may also form an N-bound, saturated 5- to     8-membered heterocycle, which in addition to the nitrogen atom may     have 1 or 2 further heteroatoms or heteroatom moieties selected from     O, S(═O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein     the N-bound heterocycle is unsubstituted or substituted with one or     more, same or different substituents selected from halogen,     C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; -   each R^(O) is independently H, CN, OH, C₁-C₆-alkyl, C₂-C₆-alkenyl,     C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which     groups are unsubstituted or substituted with halogen;     -   phenyl or benzyl, wherein the phenyl ring is unsubstituted or         substituted with one or more, same or different substituents         R^(F); -   each R^(F) is independently halogen, N₃, OH, CN, NO₂, SCN, SF₅,     C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆     alkoxy-C₁-C₄ alkyl, C₁-C₆ alkoxy-C₁-C₄ alkoxy, C₃-C₆ cycloalkyl,     C₃-C₆ cycloalkoxy, C₃-C₆ cycloalkyl-C₁-C₄ alkyl, C₃-C₆     cycloalkoxy-C₁-C₄ alkyl, which groups are unsubstituted or     substituted with halogen; -   R^(W) is C₁-C₆-alkyl, C₃-C₆-cycloalkyl,     C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are halogenated or     non-halogenated; CH₂R⁶, or phenyl, which is unsubstituted or     substituted with R¹¹ _(;) -   the index n is 0, 1, 2, 3, or 4 if G is phenyl or a 6-membered     hetaryl; or 0, 1, 2, or 3 if G is a 5-membered hetaryl; and -   the index m is 0, 1 or 2; -   and the N-oxides, stereoisomers, tautomers and agriculturally or     veterinarily acceptable salts thereof.

The compounds of the formula (I), and their agriculturally acceptable salts are highly active against animal pest, i.e. harmful arthropodes and nematodes, especially against insects and acaridae which are difficult to control by other means.

Moreover, the present invention relates to and includes the following embodiments:

-   compositions comprising at least one compound of formula (I) as     defined above and a liquid or solid carrier; -   agricultural and veterinary compositions comprising an amount of at     least one compound of formula (I) or an enantiomer, diasteromer or     salt thereof as defined above; -   methods for combating invertebrate pests, infestation, or infection     by invertebrate pests, which method comprises contacting said pest     or its food supply, habitat or breeding grounds with a pesticidally     effective amount of at least one compound of formula (I) as defined     above or a composition thereof; -   methods for controlling invertebrate pests, infestation, or     infection by invertebrate pests, which method comprises contacting     said pest or its food supply, habitat or breeding grounds with a     pesticidally effective amount of at least one compound of     formula (I) as defined above or a composition comprising at least     one compound of formula (I); -   methods for preventing or protecting against invertebrate pests     comprising contacting the invertebrate pests, or their food supply,     habitat or breeding grounds with compounds of formula (I) as defined     above or a composition comprising at least one compound of     formula (I) as defined above; -   methods for protecting crops, plants, plant propagation material     and/or growing plants from attack or infestation by invertebrate     pests comprising contacting or treating the crops, plants, plant     propagation material and growing plants, or soil, material, surface,     space, area or water in which the crops, plants, plant propagation     material is stored or the plant is growing, with a pesticidally     effective amount of at least one compound of formula (I) as defined     above or a composition comprising at least one compound of formula     (I); -   non-therapeutic methods for treating animals infested or infected by     parasites or preventing animals of getting infected or infested by     parasites or protecting animals against infestation or infection by     parasites which comprises orally, topically or parenterally     administering or applying to the animals a parasiticidally effective     amount of a compound of formula (I) as defined above or a     composition comprising at least one compound of formula (I); -   methods for treating, controlling, preventing or protecting animals     against infestation or infection by parasites by administering or     applying orally, topically or parenterally to the animals a compound     of the general formula (I) as defined above or a composition     comprising at least one compound of formula (I); -   seed comprising a compound of formula (I) as defined above, in an     amount of from 0.1 g to 10 kg per 100 kg of seed; -   the use of the compounds of formula (I) as defined above for     protecting growing plants or plant propagation material from attack     or infestation by invertebrate pests; -   the use of compounds of formula (I) or the enantiomers,     diastereomers or veterinary acceptable salts thereof for combating     parasites in and on animals; -   a process for the preparation of a veterinary composition for     treating, controlling, preventing or protecting animals against     infestation or infection by parasites which comprises adding a     parasiticidally effective amount of a compound of formula (I) or the     enantiomers, diastereomers and/or veterinary acceptable salt thereof     to a carrier composition suitable for veterinary use; -   the use of a compound of formula (I) or the enantiomers,     diastereomers and/or veterinary acceptable salt thereof for the     preparation of a medicament for treating, controlling, preventing or     protecting animals against infestation or infection by parasites.

All the compounds of formula (I) and, if applicable, their stereoisomers, their tautomers, their salts or their N-oxides as well as compositions thereof are particularly useful for controlling invertebrate pests, in particular for controlling arthropods and nematodes and especially insects. Therefore, the invention relates to the use of a compound of formula (I) as an agrochemical pesticide, preferably for combating or controlling invertebrate pests, in particular invertebrate pests of the group of insects, arachnids or nematodes.

The term “compound(s) according to the invention” or “compound(s) of formula (I)” as used in the present invention refers to and comprises the compound(s) as defined herein and/or stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) thereof. The term “compound(s) of the present invention” is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising stereoisomer(s), salt(s), tautomer(s) or N-oxide(s) of compounds of formula (I).

The term “composition(s) according to the invention” or “composition(s) of the present invention” encompasses composition(s) comprising at least one compound of formula (I) according to the invention as defined above, therefore also including a stereoisomer, an agriculturally or veterinary acceptable salt, tautomer or an N-oxide of the compounds of formula (I).

The compounds of the present invention may be amorphous or may exist in one or more different crystalline states (polymorphs) or modifications which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula (I), mixtures of different crystalline states or modifications of the respective compound I, as well as amorphous or crystalline salts thereof.

The compounds of the formula (I) may have one or, depending on the substitution pattern, more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the single pure enantiomers or pure diastereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures. Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group. The term “stereoisomer(s)” encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers). The present invention relates to every possible stereoisomer of the compounds of formula (I), i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.

Depending on the substitution pattern, the compounds of the formula (I) may be present in the form of their tautomers. Hence the invention also relates to the tautomers of the formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.

Salts of the compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality or by reacting an acidic compound of formula (I) with a suitable base.

Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH₄ ⁺) and substituted ammonium in which one to four of the hydrogen atoms are replaced by C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The term “N-oxide” includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

The organic moieties groups mentioned in the above definitions of the variables are — like the term halogen — collective terms for individual listings of the individual group members. The prefix C_(n)-C_(m) indicates in each case the possible number of carbon atoms in the group. “Halogen” will be taken to mean F, Cl, Br, and I, preferably F.

The term “substituted with”, e.g. as used in “partially, or fully substituted with” means that one or more, e.g. 1, 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by one or more, same or different substituents, such as a halogen, in particular F. Accordingly, for substituted cyclic moieties, e.g. 1-cyanocyclopropyl, one or more of the hydrogen atoms of the cyclic moiety may be replaced by one or more, same or different substituents.

The term “C_(n)-C_(m)-alkyl” as used herein (and also in C_(n)-C_(m)-alkylamino, di-C_(n)-C_(m)-alkylamino, C_(n)-C_(m)-alkylaminocarbonyl, di-(C_(n)-C_(m)-alkylamino)carbonyl, C_(n)-C_(m)-alkylthio, C_(n)-C_(m)-alkylsulfinyl and C_(n)-C_(m)-alkylsulfonyl) refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. C₁-C₄-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

The term “C_(n)-C_(m)-haloalkyl” as used herein (and also in C_(n)-C_(m)-haloalkylsulfinyl and C_(n)-C_(m)-haloalkylsulfonyl) refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C₁-C₄-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term C₁-C₁₀-haloalkyl in particular comprises C₁-C₂-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1, 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.

Similarly, “C_(n)-C_(m)-alkoxy” and “C_(n)-C_(m)-alkylthio” (or C_(n)-C_(m)-alkylsulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen (or sulfur linkages, respectively) at any bond in the alkyl group. Examples include C₁-C₄-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further C₁-C₄-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

Accordingly, the terms “C_(n)-C_(m)-haloalkoxy” and “C_(n)-C_(m)-haloalkylthio” (or C_(n)-C_(m)-haloalkyl-sulfenyl, respectively) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C₁-C₂-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy, further C₁-C₂-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio and the like. Similarly, the terms C₁-C₂-fluoroalkoxy and C₁-C₂-fluoroalkylthio refer to C₁-C₂-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.

The term “C₂-C_(m)-alkenyl” as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.

The term “C₂-C_(m)-alkynyl” as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.

The term “C_(n)-C_(m)-alkoxy-C_(n)-C_(m)-alkyl” as used herein refers to alkyl having n to m carbon atoms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radical is replaced by an C_(n)-C_(m)-alkoxy group; wherein the value of n and m of the alkoxy group are independently chosen from that of the alkyl group.

The suffix “-carbonyl” in a group or “C(═O)” denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C═O group. This is the case e.g. in alkylcarbonyl, haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl.

The term “aryl” as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl (also referred as to C₆H₅ as subsitituent).

The term “C₃-C_(m)-cycloalkyl” as used herein refers to a monocyclic ring of 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

The term “alkylcycloalkyl” denotes as well as the term “alkyl which may be substituted with cycloalkyl” an alkyl group which is substituted with a cycloalkyl ring, wherein alkyl and cycloakyl are as herein defined.

The term “cycloalkylalkyl” denotes as well as the term “cycloalkyl which may be substituted with alkyl” a cycloalkyl ring which is substituted with an alkyl group, wherein alkyl and cycloakyl are as herein defined.

The term “alkylcycloalkylalkyl” denotes as well as the term “alkylcycloalkyl which may be substituted with alkyl” an alkylcycloalkyl group which is substituted with an alkyl, wherein alkyl and alkylcycloakyl are as herein defined.

The term “ C₃-C_(m)-cycloalkenyl” as used herein refers to a monocyclic ring of 3- to m-membered partially unsaturated cycloaliphatic radicals.

The term “cycloalkylcycloalkyl” denotes as well as the term “cycloalkyl which may be substituted with cycloalkyl” a cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members and the cycloalkyls are linked through one single bond or have one common carbon atom. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (e.g. 1,1′-bicyclopropyl-2-yl), cyclohexylcyclohexyl wherein the two rings are linked through one single common carbon atom (e.g. 1,1′-bicyclohexyl-2-yl), cyclohexylcyclopentyl wherein the two rings are linked through one single bond (e.g. 4-cyclopentylcyclohexyl) and their different stereoisomers such as (1R,2S)-1, 1′-bicyclopropyl-2-yl and (1R,2R)-1,1′-bicyclopropyl-2-yl.The term “carbocycle” or “carbocyclyl” includes, unless otherwise indicated, in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms.

The carbocyclic radicals may be saturated, partially unsaturated, or fully unsaturated. Preferably, the term “carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above, for example cyclopropane, cyclobutane, cyclopentane and cyclohexane rings. When it is referred to “fully unsaturated” carbocycles, this term also includes “aromatic” carbocycles. In certain preferred embodiments, a fully unsaturated carbocycle is an aromatic carbocycle as defined below, preferably a 6-membered aromatic carbocycle.

The term “hetaryl” or “aromatic heterocycle” or “aromatic heterocyclic ring” includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H-or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or 4H-1,2,4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl. The term “hetaryl” also includes bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1, 2 or 3 heteroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.

The terms “heterocycle”, “heterocyclyl” or “heterocyclic ring” includes, unless otherwise indicated, in general 3- to 12-membered, preferably 3- to 8-membered, 3- to 7-membered, or 5-to 8-membered, more preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic radicals. The heterocyclic radicals may be saturated, partially unsaturated, or fully unsaturated. As used in this context, the term “fully unsaturated” also includes “aromatic”. In a preferred embodiment, a fully unsaturated heterocycle is thus an aromatic heterocycle, preferably a 5- or 6-membered aromatic heterocycle comprising one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, O and S as ring members. Examples of aromatic heterocycles are provided above in connection with the definition of “hetaryl”. Unless otherwise indicated, “hetaryls” are thus covered by the term “heterocycles”. The heterocyclic non-aromatic radicals usually comprise 1, 2, 3, 4 or 5, preferably 1, 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO₂. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetra-hydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpho-linyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.

The erms “alkylene”, “alkenylene”, and “alkynylene” refer to alkyl, alkenyl, and alkynyl as defined above, respectively, which are bonded to the remainder of the molecule, via two atoms, preferably via two carbon atoms, of the respective group, so that they represent a linker between two moieties of the molecule. In particular, the term “alkylene” may refer to alkyl chains such as CH₂CH₂, —CH(CH₃)—, CH₂CH₂CH₂, CH(CH₃)CH₂, CH₂CH(CH₃), CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂, and CH₂CH₂CH₂CH₂CH₂CH₂CH₂. Similarly, “alkenylene” and “alkynylene” may refer to alkenyl and alkynyl chains, respectively.

The term “5- to 6-membered carbocyclic ring” as used herein refers to cyclopentane and cyclohexane rings.

Examples of 5- or 6-membered saturated heterocyclic rings include: 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin 5 yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,-1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl.

Examples of 5- or 6-membered partially unsaturated heterocyclyl or heterocyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3 dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1,3,5-di- or tetrahydrotriazin-2-yl.

Examples of 5- or 6-membered fully unsaturated heterocyclic (hetaryl) or heteroaromatic rings are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

A “C₂-C_(m)-alkylene” is divalent branched or preferably unbranched saturated aliphatic chain having 2 to m, e.g. 2 to 7 carbon atoms, for example CH₂CH₂, —CH(CH₃)—, CH₂CH₂CH₂, CH(CH₃)CH₂, CH₂CH(CH₃), CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂, CH₂CH₂CH₂CH₂CH₂CH₂, and CH₂CH₂CH₂CH₂CH₂CH₂CH₂.

The term “alkylamino” as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, which is bonded via a nitrogen atom, e.g. an —NH— group.

The term “dialkylamino” as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, which is bonded via a nitrogen atom, which is substituted by another straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, e.g. a methylamino or ethylamino group.

The term “alkylthio “( alkylsulfanyl: alkyl-S-)” as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C₁-C₄-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom. Examples include methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

The term “haloalkylthio” as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Examples include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio and the like.

The term “alkylsulfinyl” (alkylsulfoxyl: C₁-C₆-alkyl—S(═O)—), as used herein refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C₁-C₄-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group.

The term “alkylsulfonyl” (alkyl—S(═O)₂—) as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C₁-C₄-alkylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.

The term “alkylcarbonyl” (C₁—C₆—C(═O)—) refers to a straight-chain or branched alkyl group as defined above, which is bonded via the carbon atom of a carbonyl group (C═O) to the remainder of the molecule.

The term “alkoxycarbonyl” refers to an alkoxygroup group as defined above, which is bonded via the carbon atom of a carbonyl group (C═O) to the remainder of the molecule.

The term “alkylaminocarbonyl” (C₁-C₆—NH—C(═O)—) refers to a straight-chain or branched alkylamino group as defined above, which is bonded via the carbon atom of a carbonyl group (C═O) to the remainder of the molecule. Similarly, the term “dialkylaminocarbonyl” refers to a straight-chain or branched saturated alkyl group as defined above, which is bonded to a nitrogen atom, which is substituted with another straight-chain or branched saturated alkyl group as defined above, which nitrogen atom in turn is bonded via a carbonyl group (C═O) to the remainder of the molecule.

PREPARATION METHODS

The compounds of formula (I) can be prepared by standard methods of organic chemistry. If certain derivatives cannot be prepared by the processes outlined below, they can be obtained by derivatization of other compounds of formula (I) that are accessible by these methods.

Preparation methods that are generally useful for the preparation of compounds of formula (I) have been disclosed in WO2017/167832A1, especially p.4-6 and in the experimental section, in the Iinternational Patent Application Number PCT/EP2020/082186, and in European Patent Application Number 2115353132.2, p.21-34 and the experimental section. In the following depicted Processes and Schemes, variables of formulae have a meaning as defined for formula (I) if not described otherwise. The variable “LG” refers to a leaving group, such as Cl, Br, I, triflate, tosylate etc..

Compounds (3), falling under the definition of compounds (I) wherein Q is C(R⁶), may be prepared by reaction of compounds (1) with compounds (2) as displayed under Process 1.

Reactions of this type have been described in EP3257853A1 and WO2018206479. The reaction is typically carried out under elevated temperatures of from 50-160° C. in an inert solvent. Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, or halogenated aromatic C₆-C₁₀-hydrocarbons, such as CH₂CI₂, CHCl₃, CCl₄, CH₂ClCH₂Cl, CCl₃CH₃, CHCl₂CH₂Cl, CCl₂CCl₂, or chlorobenzene; ethers, such as CH₃CH₂OCH₂CH₃, (CH₃)₂CHOCH(CH₃)₂, CH₃OC(CH₃)₃ (MTBE), CH₃OCH₃ (DME), CH₃OCH₂CH₂OCH₃, CH₃OC(CH₃)₂CH₂CH₃, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofurane (THF), and diethylene glycol; nitriles, such as CH₃CN, and CH₃CH₂CN; alcohols, such as CH₃OH, CH₃CH₂OH, CH₃CH₂CH₂OH, CH₃CH(OH)CH₃, CH₃(CH₂)₃OH, and C(CH₃)₃OH, CH₂(OH)CH₂(OH), CH₃CH(OH)CH₂OH; amides and urea derivatives, such as dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMA), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), hexamethylphosphamide (HMPA); moreover dimethyl sulfoxide (DMSO), sulfolane, and water. Mixtures of the above solvents are also possible.

The reaction may be carried out in the presence of a catalyst, such as an acid or a base, preferably a base. Suitable bases are, in general, inorganic bases, such as LiOH, NaOH, KOH, and Ca(OH)₂; alkali metal and alkaline earth metal oxides, such as Li₂O, Na₂O, CaO, and MgO; alkali metal and alkaline earth metal hydrides, such as LiH, NaH, KH and CaH₂; alkali metal and alkaline earth metal carbonates, such as Li₂CO₃, K₂CO₃ and CaCO₃; alkali metal bicarbonates, such as NaHCO₃; organic bases, such as pyrrolidine; tertiary amines, such as diisopropylethylamine, trimethylamine, triethylamine, triisopropylamine and N-methylpiperidine, imidazol, pyridine; substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and polycyclic amides and amidines, such as 1,8-diazabicycloundec-7-ene (DBU), 1,4-Diazabicyclo[2.2.2]octane (DABCO); alkali metal salts of secondary amines, such as alkali diisopropylamide, alkali bis(trimethylsilytetramethylpiperidinemethylpiperidene; alcoholates, such as alkali methanolate, alkali ethanolate, alkali isopropanolate, alkali tert-butanolate; alkali metal —alkyl, and alkali metal — aryl salts, such as n-butyl lithium, tert-butyl lithium, phenyl lithium. Mixtures of the aforementioned bases are also possible. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.

Compounds (1) can be prepared as described in WO2017/167832A1, e.g. Example C-1. Compounds (1) and compounds (2) are typically reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of compounds (2).

Compounds of formula (4), corresponding to compounds of formula (I) wherein Q is N(R⁵) can be prepared by reaction of compounds of formula (5) with compounds of formula (6), as shown under Process 2 below.

Reactions of this type have been described in EP3257853A1, WO2019/234160 and WO2016162318A1. The reaction is typically carried out at elevated temperatures, e.g. 60 to 160° C., in an inert solvent, optionally in the presence of an acid, or a coupling agent and a base. Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, or halogenated aromatic C₆-C₁₀-hydrocarbons, such as CH₂CI₂, CHCl₃, CCl₄, CH₂ClCH₂Cl, CCl₃CH₃, CHCl₂H₂Cl, CCl₂CCl₂, or chlorobenzene; ethers, such as CH₃CH₂OCH₂CH₃, (CH₃)₂CHOCH(CH₃)₂, CH₃OC(CH₃)₃ (MTBE), CH₃OCH₃ (DME), CH₃OCH₂CH₂OCH₃, CH₃OC(CH₃)₂CH₂CH₃, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofurane (THF), and diethylene glycol; nitriles, such as CH₃CN, and CH₃CH₂CN; alcohols, such as CH₃OH, CH₃CH₂OH, CH₃CH₂CH₂OH, CH₃CH(OH)CH₃, CH₃(CH₂)₃OH, and C(CH₃)₃OH, CH₂(OH)CH₂(OH), and CH₃CH(OH)CH₂OH.. Mixtures of the above solvents are also possible. Suitable acids are in general inorganic acids such as HF, HCl, hBr, H₂SO₄ and HClO₄; Lewis acids, such as BF₃, AlCl₃, FeCl₃, SnCl₄, TiCl₄ and ZnCl₂, moreover organic acids such as HCOOH, CH₃COOH, CH₃CH₂COOH, oxalic acid, toluene sulphonic acid, benzene sulphonic acid, camphor sulphonic acid, citric acid, and CF₃COOH.

Suitable coupling agents are selected from carbodiimides, such as DCC (dicyclohexylcarbodiimide) and DIC (diisopropylcarbodiimide), benzotriazole derivatives, such as HATU (O-(7-azabenzotri′zo′-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate), HBTU ((Obenzotri′zo′-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate) and HCTU (1H-benzotriazolium-1-[bis(dimethylamino)methylene]-5-chloro tetrafluoroborate) and phosphonium-derived activators, such as BOP ((benzotriazol-1-yloxy)-tris(dimethylamino) phosphonium hexafluorophosphate), PyBOP ((benzotriazol-1-yloxy)-tripyrrolidinphosphonium hexafluorophosphate) and PyBrOP (bromotripyrrolidinphosphonium hexafluorophosphate). In case a coupling agent is applied, suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, or halogenated aromatic C₆-C₁₀-hydrocarbons, such as CH₂Cl₂, CHCl₃, CCl₄, CH₂ClCH₂Cl, CCl₃CH₃, CHCl₂CH₂Cl, CCl₂CCl₂, or chlorobenzene; ethers, such as CH₃CH₂OCH₂CH₃, (CH₃)₂CHOCH(CH₃)₂, CH₃OC(CH₃)₃ (MTBE), CH₃OCH₃ (DME), CH₃OCH₂CH₂OCH₃, CH₃OC(CH₃)₂CH₂CH₃, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofurane (THF), and diethylene glycol; nitriles, such as CH₃CN, and CH₃CH₂CN; alcohols, such as CH₃OH, CH₃CH₂OH, CH₃CH₂CH₂OH, CH₃CH(OH)CH₃, CH₃(CH₂)₃OH, and C(CH₃)₃OH, CH₂(OH)CH₂(OH), and CH₃CH(OH)CH₂OH. Mixtures of the above solvents are also possible. Suitable bases are those listed for Process 1.

Alternatively, compounds (6) may be replaced by their corresponding carbonic acid halogenides, e.g. acid chlorides. In this case the reaction is typically carried out in the presence of a base. Suitable bases are those listed for Process 1 above.

In a first step, compounds (7) are thus obtained, which undergo in a second step a condensation reaction as described for Process 1 to yield compounds (4).

Compounds (5) and compounds (6) are typically reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of compounds (6).

Compounds of formula (6) may be prepared in analogy to those as described in EP3257853A1, p.51-53 by modification of the starting materials, or as described in WO2018/153778, p.14 ff and Scheme 4. Compounds of formula (5) can be prepared as described in WO2017/167832A1, Bashandy et al. Journal of Enzyme Inhibition and Medicinal Chemistry, 29(5), 619-627, 2014.

Alternatively, Compounds of formula (4) may be prepared by a two-step reaction, comprising of a reaction of compounds of formula (8) with compounds of formula (9) to yield compounds of formula (10) as displayed under Process 3

This reaction may be carried out under the same conditions as described for Process 2 above. In a second step, compounds of formula (10) are then reacted with a compound of formula (11) to yield compounds of formula (4), falling under the definition of compounds of formula (I), as displayed under Process 4.

Reactions of this type have been described in WO2016162318A1, p.89. The reaction is typically carried out at a temperature of from 15 to 60° C. in an inert solvent in the presence of a base. Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; or aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene;. Mixtures of the above solvents are also possible. Suitable bases are, in general, inorganic bases, preferably alkali metal and alkaline earth metal hydrides, such as LiH, NaH, KH and CaH₂; organic bases, preferably secondary amines, such as pyrrolidine; or tertiary amines, such as diisopropylethylamine, trimethylamine, triethylamine, triisopropylamine and N-methylpiperidine , imidazol, pyridine; substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and polycyclic amides and amidines, such as 1,8-diazabicycloundec-7-ene (DBU), 1,4-Diazabicyclo[2.2.2]octane (DABCO); or alkali metal salts of secondary amines, such as alkali diisopropylamide, alkali bis(trimethylsilyl)amide, alkali tetramethylpiperidene; alcoholates, such as alkali methanolate, alkali ethanolate, alkali isopropanolate, alkali tert-butanolate; alkali metal — alkyl, and alkali metal — aryl salts, such as n-butyl lithium, tert-butyl lithium, phenyl lithium. The base is typically reacted with compounds of formula (11) before compounds of formula (10) are added to form the thiolate anion.

The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.

Compounds (4) may also be prepared from compounds (12) as displayed below under Process 5 in a rearrangement reaction.

wherein the rings A and B are fully unsaturated.

Reactions of this type have been described in Potts K.T., Surapaneni C.R., 1970, Journal of Heterocyclic Chemistry, or Nagamatsu T., Fujita T., 2002, Heterocycles, 57(4), 631-636. The reaction is typically carried out in the presence of a catalyst, usually an acid or a base, such as NaOH or formic acid, in an inert organic solvent or H₂O at a temperature of from 0 to 80° C. If no catalyst is used, the reaction may be carried out at elevated temperatrues, e.g. from 30 to 100° C.

Compounds of formula (12) may be prepared by reaction of hydrazine compounds of formula (13) with Lewis acids, as displayed under Process 6,

wherein the rings A and B are fully unsaturated. Reactions of this type have been described by Glushkov V.A. et al., 1998, Pharmaceutical Chemistry Journal, vol.32(5), p.29-32, or WO2012148808, p.143. The reaction is typically performed in the presence of a Lwis acid, such as FeCl₃ or AlCl₃, at elevated temperatures of from 50 to 150° C. in an inert organic solvent. The reaction may be carried out in the presence of an oxidizing agent, e.g. H₂O₂ or CuCl₂.

Compounds of formula (13) are accessible by reaction of hydrazine compounds of formula (14) with aldehyde compounds of formula (15), as displayed under Process 7.

wherein ring A is fully unsaturated.

The reaction is typically carried out in the presence of an acid catalyst, such as toluene sulfonic acid, in an inert organic solvent. Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane, or petrol ether; or aromatic hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene;. Mixtures of the above solvents are also possible

Hydrazine derivatives of formula (10) are commercially available or may be derived from commercially available compounds. Alternatively, compounds of formula (14) may also be prepared by reaction of hydrazine with compound of formula (16), as displayed under Process 8.

wherein ring A is fully unsaturated.

Typical leaving groups LG are triflate, iodide and chloride. Reactions of this type have been described in Mao, Y. et al, 2014, Journal of Heterocyclic Chemistry, 51(3), p.594-597. The reaction is typically carried out in a polar solvent, such as CH₃CH2OH under elevated temperatures, such as from 50 to 100° C. Compounds of formula (15) are commercially available or can be prepared by standard methods of organic chemistry.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds of formula (I) with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds of formula (I) apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.

In an alternative synthesis route, the Processes 1, 2, 5, 6, and 7 may be modified in such a way that educts are used that have (a) leaving group(s) LG instead of substituents (R^(x))_(n) at ring G. Processes 9-13 below illustrate the modified Processes 1, 2, 5, 6, and 7..

Such Processes 9-13 may be carried out under the same conditions as described for Processes 1, 2, 5, 6, and 7. Coumpounds of formulae (17) and (20) are valuable educts in cross-coupling reactions to yield compounds of formula (I) as described below. Compounds of formulae (16), (18), and (25) are commercially available, or can be prepared by standard methods of organic chemistry. For example, compounds of formula (18) may be prepared as described in WO2016/026848, p.18-19 and Scheme 10b. Compounds of formula (18) may then be converted into compounds of formulae (16) or (25) by standard synthesis methods.

Accordingly. compounds of formula (26), corresponding to compounds of formula (I) wherein R^(X) is —C(CN)R⁷R⁸, may be obtained by methods described below in General Scheme 1.

Compounds of formula (28) can be obtained by the treatment of compounds of formula (27) wherein X can be Cl, Br, I, -OTf (triflate), by displacement reaction with HS—R^(W) in the presence of a base e.g. potassium carbonate, sodium carbonat, cesium carbonate, sodium hydride etc in an organic solvent like DMF, THF and DMSO at cooling to 20 to 25° C. Such method has been described in literature like Tetrahedron Letters, 2014, vol. 55, # 22, p. 3295 - 3298. Compounds of formula (29) may be prepared by reaction of compounds of formula (28) with Grignard reagent MeMgBr in an organic solvent like THF, MTBE or toluene at 0° C. as described in WO 2018095795, WO 2016012395 and Tetrahedron Letters 1981, vol. 22, 3815-3818.

Compounds of formula (31) can be prepared by reacting compounds of formula (29) with compounds of formula (30) wherein R^(Y) stands preferably for ethyl, methyl or tert-butyl. This reaction can be done in in polar aprotic solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), or N-methyl pyrrolidone (NMP), in the presence of a base, such as K₂CO₃ or Cs₂CO₃, in the presence of absence of a phase-transfer catalyst (“PTC”) preferably at temperature between 80-140° C. Such method is described in literature in the Journal of Organic Chemistry, 2008, vol. 73, # 4, 1643-1645 and Chemical & Pharmaceutical Bulletin ,1988, vol. 36, #. 5, 1664-8.

Compounds of formula (31) can be further converted to compounds of formula (32) via a Krapcho-Decarboxylation using LiCI or NaCl using polar organic solvents like DMSO within a temperature range of 100-140° C.

Compounds of formula (31) can also be prepared via palladium-catalysed reaction of compounds of formula (29) with trimethylsilyl-acetonitrile as described in Angew. Chem Int. Ed. 2011, vol. 50, 4470-4474.

Compounds of formula (33) can be synthesized via reaction of compounds of formula (32) with compounds R⁷-LG and R⁸-LG. The reaction is typically carried out in the presence of bases like Cs₂CO₃, K₂CO₃, Na₂CO₃, potassium tert.-butoxide, NaH, LiHMDS at 0° C. to 25° C. using polar protic solvents like DMF, DMSO, THF or N-methylpyrrolidone (NMP). Such methods have been described in literature like WO2013067264 A1 or Tetrahedron Letters, 2018, vol. 59, #.14, 1443-1445.

The sulfanyl-group R^(W)—S— in compounds of formula (33) can be further oxidised to SO (sulfoxide) and/or SO₂ (sulfone), in an oxidation reaction of compounds of formula (33) involving reagents such as, m-chloroperoxybenzoic acid, H₂O₂, oxone, NaIO₄, NaOCI or tert-butyl hypochlorite and in organic solvents including aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; and alcohols such as methanol and ethanol; acetic acid; water. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds of formula (I) to produce the sulfoxide compounds of formula (34), and preferably 2 to 2.2 moles of oxidant, relative to 1 mole of the sulfide compounds of formula (33) as descried in WO 2015/091945 Al, WO 2016107742 and WO 2018095795.

Compounds of formula (35), falling under the definition of compounds of formula (2), can be prepared by dissolving compounds of formula (34) in polar organic solvents like ethyl acetate, chloroform or DCM and reaction with brominating agents like CuBr, CuBr₂, Br₂, HBr in acetic acid, trimethyl phenyl ammonium tribromide at 20 to 25° C. or on heating to 60° C. to obtain compounds of formula (35). Such procedure can be found in WO 2016107742.

Reaction condition for the synthesis of compounds of formula (26) form compounds of formula (25) and compounds of formula (2) have been described for Process 1 above.

Alternatively compounds of formula (26), falling under the definition of compounds of formula (I) can be prepared from compounds of formula (36) in a Pd-catalyzed reaction with trimethylsilylacetonitrile (TMS-ACN). Such reactions have for example been described in Angew. Chem Int. Ed. 2011, vol. 50, 4470-4474. Compounds of formula (36) may be prepared as described in Process 9 above or as described in in WO 2017/167832 Al and WO 2018/206479 Al). Further alkylation of compounds of formula (26) with compounds of formula R⁶-LG and R⁷-LG under conditions as described above for the synthesis of compounds of formula (33) yield compounds of formula (26).

may be prepared in a sequence or reactions similar to those displayed under General Scheme 1 by replacing the reagents R⁶-LG and R⁷-LG with a reagent LG—(CH₂)_(2—5)—LG, wherein the group —(CH₂)_(2—5)— may be substituted with one or more, same or different substituents R⁹ and wherein each group LG is independently a halogen or triflate. The reaction is typically carried out in a polar solvent like CH₃CN, DMSO, THF or the like in the presence of a base, preferably an inorganic base like K3CO3 at a temperature of from 10 to 40° C.

Compounds of formula (35) fall under the definition of compounds of formula (2). Accordingly, compounds of formula (6), wherein R^(X) is —C(CN)R⁷R⁸ or wherein R^(X) is substituted C₃-C₆-cycloalkyl as defined in the claims, may be prepared in analogy to the preparation steps displayed in General Scheme 1 above, by replacing the Grignard-reaction of compounds of formula (28) with the hydrolysis of the cyano-group as displayed for example in Process 14 below. The resulting carboxylic acid group may be protected in the form of an ester.

Compounds of formula (I), wherein R^(X) is —C(R^(O))═N—N(R^(M)R^(N)) or —C(R^(O))═N—O(R^(L)) may be prepared by the methods described above by using compounds of formulae (2), (6), (8), or (15) having these substituents, or by replacing the leaving group LG in compounds of formulae (17), or (20) with the respective substituent R^(X).

Compounds of formula (2) having as substituent R^(X) a group —C(R^(O))═N—N(R^(M)R^(N)) or —C(R^(o))═NO(R^(L)) may be prepared as described under General Scheme 2 below.

wherein the substituent Z is -N(R^(M)R^(N)) or -O(R^(L)), respectively.

Compounds of formula (39) can be oxidized to the corresponding sulfoxide or sulfone by oxidation reaction involving reagents such as m-chloroperoxybenzoic acid, H₂O₂, oxone, NaIO₄, NaOCI or tert-butyl hypochlorite in an inert solvent such as aliphatic halogenated hydrocarbons, e.g. CHCI3 or CH₂CI₂; alcohols such as CH₃OH and CH₃CH₂OH; CH₃COOH; or H₂O. The amount of the oxidant to be used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, relative to 1 mole of the sulfide compounds of formula (39) to produce the sulfoxide compounds of formula (40), and more preferably 2 to 2.2 moles of oxidant, relative to 1 mole of the sulfide compounds or formula (39) as descried in WO 2015/091945 Al, WO 2016107742 and WO 2018095795.

Compounds of formula (40) may then be reacted with a tin-based vinylation reagent like tributyl vinyl tin in a Pd-catalyzed Stille- type coupling reaction to afford compounds of formula (41). The reaction is carried out in the presence of a Pd-catalyst like palladium acetate, tetrakis(triphenylphosphine)palladium, di-µ-chlorobis[5-hydroxy-2-[1-(hydroxyimino-_(K)/\/)ethyl]-phenyl_(K)C]dipalladium or a similar catalyst in an inert solvent like aromatic hydrocarbons like toluene or ethers like dioxane or dimethoxy ethane at a typical temperature of from 70° C. to 110° C.

Compounds of formula (41) may then be reacted with an oxidant like sodium meta per-iodate, oxone N-methylmorpholine N-oxide in the presence of O_(S)O₄ in an inert solvent like an ether, e.g. dioxane or MTBE, at a temperature range of from 0 to 25° C. over a period of approximately one hour, as reported in WO2015138220A1 and WO2016198908A1.

Compounds of formula (42) may then be converted to the respective imine of formula (43) by reaction with a primary amine H₂NZ, such as hydroxylamine, o-alkyl hydroxylamine, hydrazine, N-alkyl hydrazine, N-acyl hydrazine in the presence of a catalyst. Suitable catalysts are Lewis-acids like trifluorotoluene sulfonic acid and bases like potassium acetate, pyridine, triethylamine, sodium methoxide in an inert solvent like aromatic hydrocarbons like toluene or alcohols, e.g. CH₃OH, CH₃CH₂OH at a temperature of from 20° C. to the refluxation temperature of the solvent. Literature reports of thesre reaction types can be found in Journal of Medicinal Chemistry (2006), 49(24), 6987-7001 and Organic Letters (2001), 3(26), 4209-4211, Journal of Organic Chemistry, 74(11), 4166-4176; 2009.

Bromination of compounds of formula (43) to compounds of formula (44) may be achieved by methods described for General Scheme 1 above, while the conversion of compounds of formula (44) to compounds fo formula (45) has been described for Process 1 above.

Modification of the above General Scheme 2 by alteration of the starting compound of formula (39) yields compounds of formula (46) - falling under the definition of compounds of formula (6), respectively, wherein R^(X) is a group —C(R^(O))═N—N(R^(M)R^(N)) or —C(R^(O))═N—O(R^(L)) as displayed under Process 15.

The replacement of the leaving group LG may also take place after the bicyclic system of compounds of formula (I) has been build-up as described under General Scheme 3 below.

The reaction conditions of the above reactions have already beend described for the analogous conversions of compounds of formula (40) to compounds of formula (43) via compounds of formula (41) and compounds of formula (42) under General Schme 2 above.

Compounds of formula (I), wherein R^(X) is —C(R^(o))═N—N(R^(M)R^(N)), —C(R^(O))═N—O(R^(L)), and wherein R° is not H, may be prepared as described for example under General Scheme 5:

Compounds of formula (17) may be converted to compounds of formula (51) by a Pd-catalyzed Stille-type cross coupling reaction with tributyl(1-ethoxyvinyl)tin in an inert solvent like aromatic hydrocarbons, such as xylene or toluene at a temperature of from 80 to 150° C.

Typical Pd-based catalysts have already been provided above for other Stille-type reactions, e.g. the conversion of compounds of formula (40) to compounds of formula (41). Compounds of formula (51) may then be reacted with a primary amine H₂NZ to yield compounds of formula (52). Such reactions may be carried out by using approaches as described in WO2018/084142 or WO2018/124129.

In case R^(o) refers to CN, the compounds may be prepared by reacting a compound of formula (37) with isopentylnitrite in the presence of a base as displayed under Process 16 below.

Such reactions have been described in WO2017/065183 and Journal of Medicinal Chemistry, 35(12), 2274-83; 1992. Suitable solvents are for example alcohols, such as CH₃OH or CH₃CH₂OH. Suitable bases are alcoholates such as sodium methanolate, sodium isobutanolate and the like.

Compounds of formula (I), wherein R^(X) is a group (l.1) may be prepared under Process 17 as follows.

The reaction is typically carried out in the presence of an oxidant, such as NaOCI or NaIO₄, in an inert polar solvent such as H₂O, alcohols like CH₃OH, CH₃CH₂OH, or ethers like dioxane or THF and at a temperature of from 0 to 50° C.

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds of formula (I) with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981) or potassium peroxymonosulfate (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.

If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds (I) apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.

Preferences

The variables have, each on their own and in combination, the following preferred meanings. Typically, the invention relates to a compound of formula (I)

wherein

-   the rings A and B are fully unsaturated; -   Y is C=X, wherein X is O or S; -   E is N(R³) or C(R⁴); -   Q is N, N(R⁵) or C(R⁶);     -   R¹ is H, halogen, C₁C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,         C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloalkoxy, C₁-C₆-sulfenyl, C₁-C₆-sulfinyl, or         C₁-C₆-sulfonyl, which groups are unsubstituted or halogenated;     -   R³, R⁵ are independently C₁-C₆-alkyl, C₁-C₆-alkoxy,         C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-al         koxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl,         C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         which are unsubstituted or halogenated;         -   C(═O)OR^(A), NR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(c),             O-C₁-C₆-alkylen-NR^(B)R^(c), C₁-C₆-alkylen-CN,             NH-C₁-C₆-alkylen-NR^(B)R^(c), C(═O)NR^(B)R^(C), C(═O)R^(D),             C(═S)R^(D), SO₂NR^(B)R^(C), S(═O)_(m)R^(E) _(;)         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   R², R⁴, R⁶ are independently H, halogen, N₃, CN, NO₂, SCN, SF₅,         C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, tri-C₁-C₆-alkylsilyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-al         koxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy,         C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxyx-C₁-C₄-alkyl,         which groups are unsubstituted or substituted with halogen,         -   C(═O)OR^(A), NR^(B)R^(C), NOR^(A), ONR^(B)R^(C),             C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C),             C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(c),             C(═O)NR^(B)R^(C), C(═O)R^(D), C(═S)R^(D), SO₂NR^(B)R^(C),             S(═O)_(m)R^(E) _(;)         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   G is phenyl, or a 5- or 6-membered hetaryl;     -   W is S, S(O), or S(O)₂;     -   R^(x) is —C(CN)R⁷R⁸, —C(R^(O))═N—N(R^(M)R^(N)),         —C(R^(O))═N—O(R^(L)); or C₃-C₆-cycloalkyl, which is substituted         with CN and which either does not have any further substituents,         or which is further substituted with one or more, same or         different substituents R⁹; or     -   R⁷, R⁸ are independently H, halogen, CN, C₁-C₆-alkyl,         C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy,         C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl,         C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl,         C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl         or C₁-C₄-alkoxycarbonyl;     -   R⁹ halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH,         C(═O)NH₂, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy,         C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl,         C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl,         C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl,         C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl,         C₁-C₄-alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino, di-(C₁₋         C₄)alkylcarbonylamino, C1-C₄-alkoxycarbonylamino, or a group         —C(R⁹¹)═NOR⁹²;         -   phenyl, which is unsubstituted or substituted with one or             more, same or different substituents selected from halogen,             CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,             C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl,             C₁-C₄-haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and             C(=0)C₁-C₄-haloalkyl; C₁-C₄-alkyl which is unsubstituted or             substituted with one or more, same or different substituents             R⁹³;         -   R⁹¹ and R⁹² are independently H, C₁-C₄-alkyl, or             C₁-C₄-haloalkyl;         -   R⁹³ is halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl,             hydroxycarbonyl, aminocarbonyl, C₁-C₄-haloal koxy,             C₁-C₄-alkoxy, C₁-C₄-haloal kylsulfanyl,             C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl,             C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl,             C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl,             di-(C₁-C₄)alkylaminocarbonyl, C₁-C₄alkylaminocarbonyl,             C₁-C₄-alkylcarbonylamino, di-(C₁-C₄)alkylcarbonylamino,             C₁-C₄-alkoxycarbonylamino, a group —C(R⁹¹)═NOR⁹²;     -   each R^(A) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         which groups are unsubstituted or substituted with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substitutents R^(F);     -   each R^(B) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are         unsubstituted or substituted with halogen;         -   phenyl or benzyl, which groups are unsubstituted or             substituted with one or more, same or different substituents             R^(F);     -   each R^(C) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         C₁-C₆-alkyl-carbonyl, or C₁-C₆-alkoxy-carbonyl, which groups are         unsubstituted or substituted with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   each moiety NR^(B)R^(C) may also form an N-bound, saturated 5-         to 8-membered heterocycle, which in addition to the nitrogen         atom may have 1 or 2 further heteroatoms or heteroatom moieties         selected from O, S(═O)_(m) and N—R′, wherein R′ is H or         C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted         or substituted with one or more, same or different substituents         selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,         C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;     -   each R^(D) is independently H, CN, OH, C₁-C₆-alkyl,         C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-al koxy-C₁-C₄-alkyl,         C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloal         koxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted         with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   each R^(E) is independently C₁-C₆-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which are unsubstituted or         substituted with halogen; or         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   each R^(L) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         which groups are unsubstituted or substituted with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substitutents R^(F);     -   each R^(M) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are         unsubstituted or substituted with halogen;         -   phenyl or benzyl, which groups are unsubstituted or             substituted with one or more, same or different substituents             R^(F);     -   each R^(N) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl,         C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloal kyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl,         C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are         unsubstituted or substituted with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   each moiety NR^(M)R^(N) may also form an N-bound, saturated 5-         to 8-membered heterocycle, which in addition to the nitrogen         atom may have 1 or 2 further heteroatoms or heteroatom moieties         selected from O, S(═O)_(m) and N—R′, wherein R′ is H or         C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted         or substituted with one or more, same or different substituents         selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,         C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;     -   each R^(o) is independently H, CN, OH, C₁-C₆-alkyl,         C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C ₁-C₄-alkyl,         C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl,         C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or         substituted with halogen;         -   phenyl or benzyl, wherein the phenyl ring is unsubstituted             or substituted with one or more, same or different             substituents R^(F);     -   each R^(F) is independently halogen, N₃, OH, CN, NO₂, SCN, SF₅,         C₁-C₆ alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl,         C₁-C₆-alkoxy-C₁-C₄ alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy,         C₃-C₆-cycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆-cycloalkyl-C₁-C₄         alkyl, C₃-C₆-cycloalkoxy-C₁-C₄ alkyl, which groups are         unsubstituted or substituted with halogen;     -   R^(W) is C₁-C₆-alkyl, C₃-C₆-cycloalkyl,         C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are halogenated or         non-halogenated;         -   benzyl, or phenyl, which is unsubstituted or substituted             with R^(F); the index n is 0, 1, 2, 3, or 4 if G is phenyl             or a 6-membered hetaryl;     -   or 0, 1, 2, or 3 if G is a 5-membered hetaryl; and     -   the index m is 0, 1 or 2;     -   and the N-oxides, stereoisomers, tautomers and agriculturally or         veterinarily acceptable salts thereof.

In one embodiment, X is O. In another embodiment of compounds of formula (I), X is S.

In one embodiment of compounds of formula (I), E is NR³ and Q is CR⁶. In another embodiment of compounds of formula (I), E is CR⁴ and Q is NR⁵. In another embodiment of compounds of formula (I), E is NR³ and Q is N.

In one embodiment of the present invention the compound of formula (I) is compound of formula (I.A), a compound (I.B) or a compound of formula (I.C).

In one embodiment the compounds of formula (I) are compounds of formula (I.A). In another embodiment, the compounds of formula (I) are compounds of formula (I.B). In another embodiment, the compounds of formula (I) are compounds of formula (I.C). In one embodiment the compounds of formula (I) are compounds of formula (I.A) or (I.B).

R¹ is H, halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy, C₁-C₆-sulfenyl, C₁-C₆-sulfinyl, or C₁-C₆-sulfonyl, which groups are unsubstituted or halogenated.

In one embodiment, R¹ is H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₁-C₃-alkoxy, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₅-cycloalkyl, C₃-C₅-cycloalkoxy, which groups are unsubstituted or halogenate. In one embodiment, R¹ is H, C₁-C₃-alkyl, or C₁-C₃-alkoxy, which groups are unsubstituted or halogenated.

In another embodiment, R¹ is H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₁-C₃-alkoxy, which groups are unsubstituted or halogenated. In another embodiment, R¹ is C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted or halogenate. In another embodiment, R¹ is C₁-C₃-haloalkyl, preferably CF₃.

R², R⁴, R⁶ are independently H, halogen, N₃, CN, NO₂, SCN, SF₅; C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, tri-C₁-C₆-alkylsilyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy, C₃-C₆-cycloal kyl-C₁-C₄-al kyl, C₃-C₆-cycloalkoxyx-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; C(=O)OR^(A), NR^(B)R^(C), NOR^(A), ONR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C), C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C), C(═O)R^(D), C(═S)R^(D), SO₂NR^(B)R^(C), S(═O)_(n)R^(E); phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, tri-C₁-C₆-alkylsilyl, C₂-C₆-alkynyl, C₁-C₃-alkoxy-C₁-C₂-alkyl, C₁-C₃-alkoxy-C₁-C₂-alkoxy, C₃-C₅-cycloalkyl, C₃-C₅-cycloalkoxy, C₃-C₅-cycloalkyl-C₁-C₂-alkyl, C₃-C₅-cycloalkoxyx-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, C₂-C₆-alkynyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted or substituted with halogen. In another embodiment, R² is H, or C₁-C₃-alkyl. In another embodiment, R² is H.

R⁴ is typically H, C₁-C₃-alkyl or C₁-C₃-haloalkyl, preferably H or C₁-C₃-alkyl, most preferably H.

R⁵ is typically H, C₁,—C₃—alkyl or C₁-C₃-haloalkyl, preferably C₁-C₃-alkyl or C₁-C₃-haloalkyl.

R⁶ is typically H, C₁-C₃-alkyl or C₁-C₃-haloalkyl, preferably H or C₁-C₃-alkyl, most preferably H.

In case compounds of formula (I) are of formula (I.A), R³ is typically C₁-C₄ -alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or halogenated; phenyl or benzyl, in which groups the phenyl ring is unsubstituted or substituted with R^(F); and R⁶ is H, or C₁-C₃-alkyl or C₁-C₃-haloalkyl.

In case compounds of formula (I) are of formula (I.B), R⁴ is typically H, or C₁-C₃ alkyl, or C₁-C₃-haloalkyl; R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

Accordingly, in one embodiment, R¹ is H, C₁-C₃-alkyl, or C₁-C₃-alkoxy, which groups are unsubstituted or halogenated; and R² is H, halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, or C₂-C₃-alkynyl, which groups are unsubstituted or halogenated.

In another embodiment, R¹ is H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl; and R² is H. In another embodiment, R¹ is C₁-C₃-haloalkyl; and R² is H.

In another embodiment, R¹ is H, C₁-C₃-alkyl, or C₁-C₃-alkoxy, which groups are unsubstituted or halogenated; and R² is H, halogen,C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, or C₂-C₃-alkynyl, which groups are unsubstituted or halogenated.

In one embodiment, R⁴ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, tri-C₁-C₆-alkylsilyl, C₂-C₆-alkynyl, C₁-C₃-alkoxy-C₁-C₂-alkyl, C₁-C₃-alkoxy-C₁-C₂-alkoxy, C₃-C₅-cycloalkyl, C₃-C₅-cycloalkoxy, C₃-C₅-cycloalkyl-C₁-C₂-alkyl, C₃-C₅-cycloalkoxyx-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁴ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, C₂-C₆-alkynyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁴ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁴ is H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl. In another embodiment, R⁴ is H, or C₁-C₃-alkyl. In another embodiment, R⁴ is H.

In one embodiment, R⁶ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, tri-C₁-C₆-alkylsilyl, C₂-C₆-alkynyl, C₁-C₃-alkoxy-C₁-C₂-alkyl, C₁-C₃-alkoxy-C₁-C₂-alkoxy, C₃-C₅-cycloalkyl, C₃-C₅-cycloalkoxy, C₃-C₅-cycloalkyl-C₁-C₂-alkyl, C₃-C₅-cycloalkoxyx-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁶ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, C₂-C₆-alkynyl, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁶ is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted or substituted with halogen. In another embodiment, R⁶ is H, C₁-C₃-alkyl, C₁-C₃-haloalkyl. In another embodiment, R⁶ is H, or C₁-C₃-alkyl. In another embodiment, R⁶ is H. R³, R⁵ are independently C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, or C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which are unsubstituted or halogenated; C(=O)OR^(A), NR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C), C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C), C(═O)R^(D), C(═S)R^(D), SO₂NR^(B)R^(C), S(═O)_(n)R^(E); phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F). In one embodiment, R³ is C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, or C₁-C₃-alkoxy-C₁-C₃-alkyl which are unsubstituted or halogenated; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F). In another embodiment embodiment, R³ is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, or C₁-C₃-alkoxy-C₁-C₃-alkyl, which are unsubstituted or halogenated; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F). In another embodiment, R³ is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which are unsubstituted or halogenated; phenyl or benzyl, wherein the phenyl ring is unsubstituted or halogenated. In another embodiment, R³ is C₁-C₃-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or halogenated. In another embodiment, R³ is C₁-C₃-alkyl, preferably methyl, which are unsubstituted or halogenated.

Accordingly, in one embodiment, R³ is C₁-C₃-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or halogenated; and R⁶ is H, or C₁-C₃-alkyl or C₁-C₃-haloalkyl.

In one embodiment, R⁵ is C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, or C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which are unsubstituted or halogenated.

In another embodiment embodiment, R⁵ is C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which are unsubstituted or halogenated.

In another embodiment, R⁵ is C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, which are unsubstituted or halogenated. In another embodiment, R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl. In another embodiment, R⁵ is C₁-C₃-alkyl, preferably methyl, which are unsubstituted or halogenated.

Each R⁷is independently H, halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl.

In one embodiment, each R⁷ is independently H, halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, or C₃-C₆-cycloalkyl. In another embodiment, each R⁷ is independently C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl. In another embodiment, each R⁷ is independently H or C₁-C₆-alkyl. In another embodiment, each R⁷ is independently C₁-C₆-alkyl; preferably CH₃.

Each R⁸ is independently H, halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl. In one embodiment, each R⁸ is independently H, halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, or C₃-C₆-cycloalkyl. In another embodiment, each R⁸ is independently C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl. In another embodiment, each R⁸ is independently H or C₁-C₆-alkyl. In another embodiment, each R⁸ is independently C₁-C₆-alkyl; preferably CH₃.

Typically, R⁷ and R⁸ are both not H. Preferably, each R⁷ and R⁸ are independently selected from halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl, more preferably selected from C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, and C₁-C₄-alkoxy-C₁-C₄-alkyl, most preferably from C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, and C₁-C₄-alkoxy, especially preferably from C₁-C₆-alkyl and C₁-C₆-haloalkyl, in particular from C₁-C₃-alkyl and C₁-C₃-haloalkyl, such as from C₁-C₃-alkyl. In a particularly preferred embodiment, both R₇ and R₈ are CH₃.

Each R⁹ is independently halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH, C(═O)NH₂, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl, C₁-C₄-alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino, di-(C₁-C₄)alkylcarbonylamino, C1-C₄-alkoxycarbonylamino, or a group —C(R⁹¹)═NOR⁹²; phenyl, which is unsubstituted or substituted with one or more, same or different substituents selected from halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and C(═O)C,—C₄—haloalkyl; C₁-C₄-alkyl which is unsubstituted or substituted with one or more, same or different substituents R⁹³.

In one embodiment, each R⁹ is independently halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH, C(═O)NH₂, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl, C₁-C₄-alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino, di-(C₁-C₄)alkylcarbonylamino, C1-C₄-alkoxycarbonylamino, or a group —C(R⁹¹)═NOR⁹².

In another embodiment, each R⁹ is independently halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH, C(═O)NH₂, C₁-C₄-haloalkoxy, or C₁-C₄-alkoxy. In another embodiment, each R⁹ is independently halogen, CN, NH₂, or OH.

Each R^(A) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents R^(F).

In one embodiment, each R^(A) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₁-C₃-alkoxy-C₁-C₂-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, C₃-C₆-cycloalkoxy-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents R^(F).

In one embodiment, each R^(A) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

Each R^(B) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; C₁-C₆-alkylen-CN; phenyl and benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(B) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In another embodiment, each R^(B) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

Each R^(C) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(C) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In another embodiment, each R^(C) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl. Alternatively, each moiety NR^(B)R^(C) may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(═O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy. In one embodiment, each moiety NR^(B)R^(C) may also form an N-bound, saturated 5-to 6-membered heterocycle, wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl, C₁-C₃-alkoxy and C₁-C₃-haloalkoxy.

Each R^(D) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(D) is independently C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F). In another embodiment, each R^(D) is independently C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

Each R^(E) is indepentently C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with R^(F).

In one embodiment, each R^(E) is indepentently C₁-C₃-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl. In one embodiment, each R^(E) is indepentently C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

Each R^(F) is independently halogen, N₃, OH, CN, NO₂, SCN, SF₅; C₁-C₆ alkyl, C₁-C₆ alkoxy, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₆ alkoxy-C₁-C₄ alkyl, C₁-C₆ alkoxy-C₁-C₄ alkoxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆ cycloalkyl-C₁-C₄ alkyl, C₃-C₆ cycloalkoxy-C₁-C₄ alkyl, which groups are unsubstituted or substituted with halogen. In one embdodiment, each R^(F) is independently halogen, OH, CN, NO₂; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃ alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen. In another embdodiment, each R^(F) is independently halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃ alkenyl, C₂-C₃-alkynyl, which groups are unsubstituted or substituted with halogen. In another embodiment, each R^(F) is independently halogen, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

Each R^(L) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, R^(L) is H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In another embodiment, each R^(L) is independently H, C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl, C₃-C₆-cycloalkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

In another embodiment, each R^(L) is independently H or C,—C₃—alkyl, wherein the alkyl group is unsubstituted or substituted with halogen.ln another embodiment, each R^(L) is independently H or C₁-C₃-alkyl, wherein the alkyl group is unsubstituted. In another embodiment, each R^(L) is independently H or C₁-C₃-alkyl, wherein the alkyl group is substituted with halogen. In another embodiment, each R^(L) is independently C₁-C₃-alkyl, wherein the alkyl group is unsubstituted or substituted with halogen. In another embodiment, each R^(L) is independently H; C₁-C₃-alkyl, C₃-C₆-cycloalkyl, or C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen or CN. In another embodiment, each R^(L) is independently H; C₁-C₃-alkyl, or C₃-C₅-cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or substituted with halogen or CN.

Each R^(M) is is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(M) is independently H, C₁-C₆-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In another embodiment, each R^(M) is independently H, C₁-C₆-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen;

In another embodiment, each R^(M) is independently H or C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxycarbonyl, which groups are unsubstituted or substituted with halogen. In another embodiment, each R^(M) is independently H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In another embodiment, each R^(M) is phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

Each R^(N) is is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(N) is independently H, C₁-C₆-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F).

In another embodiment, each R^(N) is independently H, C₁-C₆-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen. In another embodiment, each R^(N) is independently H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In another embodiment, each R^(N) is independently H or C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxycarbonyl, which groups are unsubstituted or substituted with halogen.

In another embodiment, each R^(N) is phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

Alternatively, each moiety N(R^(M)R^(N)), may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(═O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy.

In one embodiment, each moiety NR^(M)R^(N) may also form an N-bound, saturated 5- to 6-membered heterocycle, wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-haloalkyl, C₁-C₃-alkoxy and C₁-C₃-haloalkoxy.

Each R^(O) is independently H, CN, OH, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F).

In one embodiment, each R^(O) is independently H, CN, or C₁-C₆-alkyl.

In another embodiment, each R^(O) is independently H or CN.

In another embodiment, each R^(O) is independently H.

In another embodiment, each R^(O) is independently C₁-C₆-alkyl.

In another embodiment, each R^(O) is independently CN. In one embodiment, R^(O) is H, CN, or C₁-C₃-alkyl (e.g. CH₃).

R^(W) is indepentently is C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are halogenated or non-halogenated; benzyl, or phenyl, which is unsubstituted or substituted with R^(F);

In one embodiment, each R^(W) is indepentently C₁-C₃-alkyl or C₃-C₆-cycloalkyl, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, and C₁-C₃-haloalkyl.

In another embodiment, each R^(W) is indepentently C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In another embodiment, each R^(W) is C₁-C₃-alkyl, which is unsubstituted or substituted with halogen. In another embodiment, R^(W) is C₁-C₃-alkyl, which is unsubstituted or substituted with halogen.

In another embodiment, each R^(W) is C₁-C₃-alkyl, preferably ethyl which is unsubstituted;

In another embodiment, each R^(W) is C₁-C₃-alkyl, which is substituted with halogen;

In another embodiment, each R^(W) is benzyl or phenyl, which is unsubstituted or substituted with R^(F) _(.)

Each R^(X) is —C(CN)R⁷R⁸, —C(R^(O))═N—N(R^(M)R^(N)), —C(R^(O))═N—O(R^(L)), C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹; or a group of formula (I.1)

wherein the ring L is a 5- or 6-membered saturated, partially or fully unsaturated carbo- or heterocycle ; wherein the ring L is a saturated, partially or fully saturated carbo- or heterocycle, which carobo-or heterocycle is unsubstituted or substituted with one or more, same or different substituents R¹⁰, and wherein said heterocycle contains one or more, same or different heteroatoms N, O, or S, and wherein said heteroatoms S and N are oxidized or non-oxidized; wherein ring J is partially or fully unsaturated and unsubstituted or substituted with one or more, same or different substituents R¹¹; and wherein “&” means the connection to the remainder of the molecule at the position of R^(X) in formula (I).

Typically, the ring L is a 5-membered saturated carbocycle, which is substituted with one or more, same or different substituents R¹⁰. In one embodiment, the ring L is a saturated 5-membered carbocycle having no substituents R¹⁰. In another embodiment, the ring L is a saturated 5-membered carbocycle having one substituent R¹⁰.

The ring J is typically partially unsaturated and has none or one substituent R¹¹, preferably none substituent R¹¹.

Each R¹⁰, R¹¹ is independently H, halogen, CN, OH; C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, or C₁-C₄-alkoxy-C₁-C₄-alkyl, which groups are unsubstituted or halogenated. Typically, each R¹⁰, R¹¹ is independently H, halogen, CN, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In one embodiment, R^(X) is —C(CN)R⁷R⁸. In another embodiment, R^(X) is —C(R^(O))═N—N(R^(M)R^(N)).

In another embodiment, R^(X) is —C(R^(O))═N—O(R^(L)). In another embodiment, R^(X) is C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹. In another embodiment, R^(X) is a group (1.1) as defined above. In another embodiment, R^(X) is —C(CN)R⁷R⁸ or C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹. In another embodiment, R^(X) is C₃-C₆-cycloalkyl, which is substituted with CN.

In another embodiment, each R^(X) is independently —C(CN)R⁷R⁸ or C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹;

-   R⁷, R⁸ are independently C₁-C₃-alkyl or C₁-C₃-haloalkyl; -   R⁹ is halogen, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In another embodiment, each R^(X) is independently —C(CN)(CH₃)₂ or cyclopropyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹; R⁹ is halogen, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

In another embodiment, each R^(X) is independently —C(R^(O))═N—O(R^(L)) or —C(R^(O))═N—N(R^(M)R^(N));

-   each R^(O) is independently H, CN, C₁-C₃-alkyl, or C₁-C₃-haloalkyl; -   each R^(L) is independently H; or C₁-C₃-alkyl, C₃-C₅-cycloalkyl,     C₃-C₅-cycloalkyl-C₁-C₃-alkyl, which groups are unsubstituted or     substituted with halogen or CN; each R^(M), R^(N) is independently     H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl;

or a group of formula (I.1), wherein the ring J is a 5- membered heterocycle; wherein the ring L is 5- or 6-membered saturated carbocycle, which is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, and C₁-C₃-haloalkyl; and wherein ring J is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, and C₁-C₃-haloalkyl.

In another embodiment, each R^(X) is independently —C(R^(O))═N—O(R^(L)) or —C(R^(O))═N—N(R^(M)R^(N));

-   each R^(O) is independently H, CN, or C₁-C₃-alkyl; -   each R^(L) is independently H; or C₁-C₃-alkyl, C₃-C₃-cycloalkyl,     C₃-C₅-cycloalkyl-C₁-C₃-alkyl, which groups are unsubstituted or     substituted with halogen or CN; each R^(M), R^(N) is independently     H, or C₁-C₃-alkyl;

or a group of formula (I.1), wherein the ring J is a 5- membered heterocycle; wherein the ring L is 5-membered saturated carbocycle.

In one embodiment, W is S, S(O), or S(O)₂. In another embodiment, W is S, S(O), or S(O)₂.

In another embodiment, W is S or S(O)₂. In another embodiment, W is S. In another embodiment, W is S(O)₂. In another embodiment, W is S(O).

In one embodiment, G is phenyl, or a 5- or 6-membered hetaryl. In another embodiment, G is phenyl. In another embodiment, G is phenyl, or 6-membered hetaryl. In another embodiment, G is a 5- or 6-membered hetaryl. In another embodiment, G is a 6-membered hetaryl. In another embodiment, G is a 5-membered hetaryl. In another embodiment, G is a 6-membered hetaryl, preferably pyridyl or pyrimidinyl. In another embodiment, G is pyridyl, pyrazinyl, or pyrimidinyl. In another embodiment, G is pyridyl or pyrazinyl. In another embodiment, G is phenyl, pyridyl, or pyrazinyl. In another embodiment, G is phenyl or pyridyl. In another embodiment, G is pyridyl, typically 2-pyridyl.

The index m is 0, 1, or 2. In one embodiment, the index m is 2. In another embodiment, the index m is 0.

In one embodiment, the index n is 0, 1, 2, 3, or 4 if G is phenyl or a 6-membered hetaryl; or 0, 1, 2, or 3 if G is a 5-membered hetaryl. In another embodiment, the index n is 1, or 2. In another embodiment, the index n is 1.

Preferred are the compound of formula (I), wherein

-   R¹ is H, C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted     or halogenated; -   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated,     preferably H.

Preferred are the compound of formula (I.A), wherein

-   R³ is C₁-C₄ -alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆     cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or     halogenated; phenyl or benzyl, in which groups the phenyl ring is     unsubstituted or substituted with R^(F); -   R⁶ is H, or C₁-C₃-alkyl or C₁-C₃-haloalkyl.

Preferred are the compound of formula (I.B), wherein

-   R⁴ is H, or C₁-C₃ alkyl, or C₁-C₃-haloalkyl; -   R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl.

Preferred are the compound of formula (I), wherein

-   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and -   m is 0 or 2.

Preferred are the compounds of formula (I), wherein R^(O) is H, CH₃, or CN, such as H or CN.

In one preferred embodiment, the compound of formula (I) is the compound of formula I.A, I.B, or I.C, wherein

-   R¹ is H, C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted     or halogenated; -   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated, -   R³ is C₁-C₄ -alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆     cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or     halogenated;     -   phenyl or benzyl, in which groups the phenyl ring is         unsubstituted or substituted with R^(F); -   R⁴ is H, C₁-C₃ alkyl, or C₁-C₃-haloalkyl; -   R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl; -   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and -   m is 0 or 2; -   R^(M) is H or C₁-C₆-alkyl-carbonyl; -   R^(N) is H or C₁-C₆-alkyl-carbonyl; -   R^(O) is H or CN.

In another preferred embodiment, the compound of formula (I) is the compound of formula I.A, wherein

-   R¹ is H, C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted     or halogenated; -   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated, -   R³ C₁-C₄ -alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆     cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or     halogenated;     -   phenyl or benzyl, in which groups the phenyl ring is         unsubstituted or substituted with R^(F); -   R⁴ is H, C₁-C₃ alkyl, or C₁-C₃-haloalkyl; -   R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl. -   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and -   m is 0 or 2; -   R^(M) is H or C₁-C₆-alkyl-carbonyl; -   R^(N) is H or C₁-C₆-alkyl-carbonyl; -   R^(O) is H or CN.

In one preferred embodiment, the compound of formula (I) is the compound of formula I.A, I.B, or I.C, wherein

-   R¹ is H, C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted     or halogenated; -   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated, -   R³ C₁-C₄-alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆     cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or     halogenated; -   phenyl or benzyl, in which groups the phenyl ring is unsubstituted     or substituted with R^(F); R⁴ is H, C₁-C₃ alkyl, or C₁-C₃-haloalkyl; -   R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl. -   R^(X) is —C(CN)R⁷R⁸, —C(R^(O))═N—O(R^(L)), or C₃-C₆-cycloalkyl,     which is substituted with CN and which either does not have any     further substituents, or which is further substituted with one or     more, same or different substituents R⁹; -   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and -   m is 0 or 2; -   R^(M) is H or C₁-C₆-alkyl-carbonyl; -   R^(N) is H or C₁-C₆-alkyl-carbonyl; -   R^(O) is H or CN.

In another preferred embodiment, the compound of formula (I) is the compound of formula I.A, wherein

-   R¹ is H, C₁-C₃-alkyl, C₁-C₃-alkoxy, which groups are unsubstituted     or halogenated; -   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated, -   R³ C₁-C₄ -alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₆ cycloalkyl, C₃-C₆     cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or     halogenated; -   phenyl or benzyl, in which groups the phenyl ring is unsubstituted     or substituted with R^(F); -   R⁴ is H,C₁-C₃ alkyl, or C₁-C₃-haloalkyl; -   R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl. -   R^(X) is —C(CN)R⁷R⁸, —C(R^(O))═N—O(R^(L)), or -   C₃-C₆-cycloalkyl, which is substituted with CN and which either does     not have any further substituents, or which is further substituted     with one or more, same or different substituents R⁹; -   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and -   m is 0 or 2; -   R^(M) is H or C₁-C₆-alkyl-carbonyl; -   R^(N) is H or C₁-C₆-alkyl-carbonyl; -   R^(O) is H or CN.

In another preferred embodiment, the compound of formula (I) is the compound of formula I.A, wherein

-   G is phenyl or pyridyl, preferably 2-pyridyl;

-   R¹ is H, C₁-C₃-alkyl or C₁-C₃-haloalkyl, which groups are     unsubstituted or halogenated, preferably CF₃;

-   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated,     preferably H;

-   R³ is C₁-C₃-alkyl, cyclopropyl, cyclopropyl-C₁-C₂-alkyl, which     groups are unsubstituted or halogenated, preferably unsubstituted;

-   R⁶ is H, CH₃, or CF₃, preferably H;

-   each R^(X) is independently —C(CN)(CH₃)₂; 1-cyano-cyclopropyl, which     is unsubstituted or which is further substituted with one or more,     same or different substituents selected from halogen, C₁-C₃-alkyl,     or C₁-C₃-haloalkyl, preferably unsubstituted;;

-   —C(R^(O))═N—O(R^(L)), or —C(R^(O))═N—N(R^(M)R^(N)), wherein     -   R^(O) is H, CN, C₁-C₃-alkyl, or C₁-C₃-haloalkyl; preferably H,         CN, or CH₃;     -   R^(L) is H;     -   C₁-C₃-alkyl, which is unsubstituted or substituted with one or         more, same or different substituents selected from halogen, and         CN; or     -   C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl;     -   Each R^(M), RN is independently H, C₁-C₃-alkyl, or         C₁-C₃-haloalkyl;     -   R^(N)

-   or a group of formula (I.2) falling under the definition of formula     (I.1)

-   

-   wherein “&” means the connection to the remainder of the molecule at     the position of R^(X) in formula (I);

-   wherein rings J, L are both independently unsubstituted or     substituted with one or more, same or different substituents     selected from halogen, CN, C₁-C₃-alkyl, and C₁-C₃-haloalkyl,     preferably unsubstituted;

-   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and

-   the index m is 0 or 2; and

-   the index n is 1.

In another preferred embodiment, the compound of formula (I) is the compound of formula I.A, wherein

-   G is phenyl or pyridyl, preferably 2-pyridyl;

-   R¹ is H, C₁-C₃-alkyl or C₁-C₃-haloalkyl, which groups are     unsubstituted or halogenated, preferably CF₃;

-   R² is H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated,     preferably H;

-   R³ is C₁-C₃-alkyl, cyclopropyl, cyclopropyl-C₁-C₂-alkyl, which     groups are unsubstituted or halogenated, preferably unsubstituted;

-   R⁶ is H, CH₃, or CF₃, preferably H;

-   each R^(X) is independently —C(CN)(CH₃)₂; 1-cyano-cyclopropyl, which     is unsubstituted or which is further substituted with one or more,     same or different substituents selected from halogen, C₁-C₃-alkyl,     or C₁-C₃-haloalkyl, preferably unsubstituted;; —C(R^(O))═N—O(R^(L)),     wherein     -   R^(O) is H, or CN;     -   R^(L) is H;     -   C₁-C₃-alkyl, which is unsubstituted or substituted with one or         more, same or different substituents selected from halogen, and         CN; or     -   C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which groups are         unsubstituted or halogenated, preferably unsubstituted;

-   or a group of formula (I.2) falling under the definition of formula     (I.1)

-   

-   wherein “&” means the connection to the remainder of the molecule at     the position of R^(X) in formula (I);

-   wherein rings J, L are both independently unsubstituted or     substituted with one or more, same or different substituents     selected from halogen, CN, C₁,-C₃-alkyl, and C₁-C₃-haloalkyl,     preferably unsubstituted;

-   R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl, and

-   the index m is 0 or 2; and

-   the index n is 1.

Compounds of formula (I) have a moiety of formula (H)

wherein all variables are defined as for formula (I) and wherein “§” means the connection to the bicyclic part of formula (I), i.e. the remainder of the molecule.

Preferably, groups H are selected from the following groups of formulae H-1 to H-144;

Typically, the moiety of formula (H) is of formula H-33 to H-41, H-81 to H-89, and H-129 to H-137, preferably of formula H-81 to H-89. In another embodiment, the moiety of formula (H) is of formula H-33 to H-48, H-81 to H-96, and H-129 to H-144. In another embodiment, the moiety of formula (H) is of formula H-33 to H-48, H-81 to H-96, H-129 to H-144, H-151 to H-153, and H-160 to H-162, preferably from H-33 to H-48, H-81 to H-88, H-91 to to H-96, H-151, H-152, H-160, and H-161, most preferably from H-33 to H-40, H-43 to H-48, H-81 to H-96, H-151, H-152, H-160, and H-161.

According to particularly preferred embodiment of the compound of formula (I), compounds of the invention are the compounds that are compiled in Tables 1 to Table 90.

Table 1. Compounds of formula I.A in which X is O, R³ is CH₃, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 2. Compounds of formula I.A in which X is O, R³ is C₂H₅, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 3. Compounds of formula I.A in which X is O, R³ is _(C)—C₃H₅, R⁶ is H and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 4. Compounds of formula I.A in which X is O, R³ is c—C₃H₅—CH₂—, R⁶ is H and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 5. Compounds of formula I.A in which X is O, R³ is CH₂CF₃, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 6. Compounds of formula I.A in which X is O, R³ is CH₃, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 7. Compounds of formula I.A in which X is O, R³ is C₂H₅, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 8. Compounds of formula I.A in which X is O, R³ is c-C₃H₅, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 9. Compounds of formula I.A in which X is O, R³ is c—C₃H₅—CH₂, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 10. Compounds of formula I.A in which X is O, R³ is CH₂CF₃, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 11. Compounds of formula I.A in which X is S, R³ is CH₃, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 12. Compounds of formula I.A in which X is S, R³ is C₂H₅, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 13. Compounds of formula I.A in which X is S, R³ is c-C₃H₅, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 14. Compounds of formula I.A in which X is S, R³ is c—C₃H₅—CH₂—, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 15. Compounds of formula I.A in which X is S, R³ is CH₂CF₃, R⁶ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 16. Compounds of formula I.A in which X is S, R³ is CH₃, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 17. Compounds of formula I.A in which X is S, R³ is C₂H₅, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 18. Compounds of formula I.A in which X is S, R³ is c-C₃H₅, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 19. Compounds of formula I.A in which X is S, R³ is c—C₃H₅—CH₂—, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 20. Compounds of formula I.A in which X is S, R³ is CH₂CF₃, R⁶ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 21. Compounds of formula I.B in which X is O, R⁴ is CH₃, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 22. Compounds of formula I.B in which X is O, R⁴ is H, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 23. Compounds of formula I.B in which X is O, R⁴ is c-C₃H₅, R⁵ is H and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 24. Compounds of formula I.B in which X is O, R⁴ is c—C₃H₅—CH₂—, R⁵ is H and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 25. Compounds of formula I.B in which X is O, R⁴ is CH₂CF₃, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 26. Compounds of formula I.B in which X is O, R⁴ is CH₃, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 27. Compounds of formula I.B in which X is O, R⁴ is H, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 28. Compounds of formula I.B in which X is O, R⁴ is c-C₃H₅, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 29. Compounds of formula I.B in which X is O, R⁴ is c—C₃H₅—CH₂, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 30. Compounds of formula I.B in which X is O, R⁴ is CH₂CF₃, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 31. Compounds of formula I.B in which X is S, R⁴ is CH₃, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 32. Compounds of formula I.B in which X is S, R⁴ is H, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 33. Compounds of formula I.B in which X is S, R⁴ is c-C₃H₅, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 34. Compounds of formula I.B in which X is S, R⁴ is c—C₃H₅—CH₂—, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 35. Compounds of formula I.B in which X is S, R⁴ is CH₂CF₃, R⁵ is H and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 36. Compounds of formula I.B in which X is S, R⁴ is CH₃, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 37. Compounds of formula I.B in which X is S, R⁴ is H, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 38. Compounds of formula I.B in which X is S, R⁴ is c-C₃H₅, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 39. Compounds of formula I.B in which X is S, R⁴ is c—C₃H₅—CH₂—, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 40. Compounds of formula I.B in which X is S, R⁴ is CH₂CF₃, R⁵ is CH₃ and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 41. Compounds of formula I.C in which X is O, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 42. Compounds of formula I.C in which X is O, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 43. Compounds of formula I.C in which X is O, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 44. Compounds of formula I.C in which X is O, R³ is c—C₃H₅—CH₂—, and the meaning for the combination of R¹, R² and moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 45. Compounds of formula I.C in which X is O, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 46. Compounds of formula I.C in which X is O, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 47. Compounds of formula I.C in which X is O, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 48. Compounds of formula I.C in which X is O, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 49. Compounds of formula I.C in which X is O, R³ is c—C₃H₅—CH₂, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 50. Compounds of formula I.C in which X is O, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 51. Compounds of formula I.C in which X is O, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 52. Compounds of formula I.C in which X is O, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 53. Compounds of formula I.C in which X is O, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 54. Compounds of formula I.C in which X is O, R³ is c—C₃H₅—CH₂, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 55. Compounds of formula I.C in which X is O, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 56. Compounds of formula I.C in which X is S, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 57. Compounds of formula I.C in which X is S, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 58. Compounds of formula I.C in which X is S, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 59. Compounds of formula I.C in which X is S, R³ is c—C₃H₅—CH₂—, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 60. Compounds of formula I.C in which X is S, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 61. Compounds of formula I.C in which X is S, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 62. Compounds of formula I.C in which X is S, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 63. Compounds of formula I.C in which X is S, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 64. Compounds of formula I.C in which X is S, R³ is c—C₃H₅—CH₂—, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 65. Compounds of formula I.C in which X is S, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 66. Compounds of formula I.C in which X is S, R³ is CH₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 67. Compounds of formula I.C in which X is S, R³ is C₂H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 68. Compounds of formula I.C in which X is S, R³ is c-C₃H₅, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 69. Compounds of formula I.C in which X is S, R³ is c—C₃H₅—CH₂—, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

Table 70. Compounds of formula I.C in which X is S, R³ is CH₂CF₃, and the meaning for the combination of R¹, R² and the moiety of formula (H) for each individual compound corresponds in each case to one line of Table A.

TABLE A Combination of meanings for R¹, R², and moiety of formula (H) Line R¹ R² H A-1 CF₃ H H-1 A-2 CF₃ H H-2 A-3 CF₃ H H-3 A-4 CF₃ H H-4 A-5 CF₃ H H-5 A-6 CF₃ H H-6 A-7 CF₃ H H-7 A-8 CF₃ H H-8 A-9 CF₃ H H-9 A-10 CF₃ H H-10 A-11 CF₃ H H-11 A-12 CF₃ H H-12 A-13 CF₃ H H-13 A-14 CF₃ H H-14 A-15 CF₃ H H-15 A-16 CF₃ H H-16 A-17 CF₃ H H-17 A-18 CF₃ H H-18 A-19 CF₃ H H-19 A-20 CF₃ H H-20 A-21 CF₃ H H-21 A-22 CF₃ H H-22 A-23 CF₃ H H-23 A-24 CF₃ H H-24 A-25 CF₃ H H-25 A-26 CF₃ H H-26 A-27 CF₃ H H-27 A-28 CF₃ H H-28 A-29 CF₃ H H-29 A-30 CF₃ H H-30 A-31 CF₃ H H-31 A-32 CF₃ H H-32 A-33 CF₃ H H-33 A-34 CF₃ H H-34 A-35 CF₃ H H-35 A-36 CF₃ H H-36 A-37 CF₃ H H-37 A-38 CF₃ H H-38 A-39 CF₃ H H-39 A-40 CF₃ H H-40 A-41 CF₃ H H-41 A-42 CF₃ H H-42 A-43 CF₃ H H-43 A-44 CF₃ H H-44 A-45 CF₃ H H-45 A-46 CF₃ H H-46 A-47 CF₃ H H-47 A-48 CF₃ H H-48 A-49 CF₃ H H-49 A-50 CF₃ H H-50 A-51 CF₃ H H-51 A-52 CF₃ H H-52 A-53 CF₃ H H-53 A-54 CF₃ H H-54 A-55 CF₃ H H-55 A-56 CF₃ H H-56 A-57 CF₃ H H-57 A-58 CF₃ H H-58 A-59 CF₃ H H-59 A-60 CF₃ H H-60 A-61 CF₃ H H-61 A-62 CF₃ H H-62 A-63 CF₃ H H-63 A-64 CF₃ H H-64 A-65 CF₃ H H-65 A-66 CF₃ H H-66 A-67 CF₃ H H-67 A-68 CF₃ H H-68 A-69 CF₃ H H-69 A-70 CF₃ H H-70 A-71 CF₃ H H-71 A-72 CF₃ H H-72 A-73 CF₃ H H-73 A-74 CF₃ H H-74 A-75 CF₃ H H-75 A-76 CF₃ H H-76 A-77 CF₃ H H-77 A-78 CF₃ H H-78 A-79 CF₃ H H-79 A-80 CF₃ H H-80 A-81 CF₃ H H-81 A-82 CF₃ H H-82 A-83 CF₃ H H-83 A-84 CF₃ H H-84 A-85 CF₃ H H-85 A-86 CF₃ H H-86 A-87 CF₃ H H-87 A-88 CF₃ H H-88 A-89 CF₃ H H-89 A-90 CF₃ H H-90 A-91 CF₃ H H-91 A-92 CF₃ H H-92 A-93 CF₃ H H-93 A-94 CF₃ H H-94 A-95 CF₃ H H-95 A-96 CF₃ H H-96 A-97 CF₃ H H-97 A-98 CF₃ H H-98 A-99 CF₃ H H-99 A-100 CF₃ H H-100 A-101 CF₃ H H-101 A-102 CF₃ H H-102 A-103 CF₃ H H-103 A-104 CF₃ H H-104 A-105 CF₃ H H-105 A-106 CF₃ H H-106 A-107 CF₃ H H-107 A-108 CF₃ H H-108 A-109 CF₃ H H-109 A-110 CF₃ H H-110 A-111 CF₃ H H-111 A-112 CF₃ H H-112 A-113 CF₃ H H-113 A-114 CF₃ H H-114 A-115 CF₃ H H-115 A-116 CF₃ H H-116 A-117 CF₃ H H-117 A-118 CF₃ H H-118 A-119 CF₃ H H-119 A-120 CF₃ H H-120 A-121 CF₃ H H-121 A-122 CF₃ H H-122 A-123 CF₃ H H-123 A-124 CF₃ H H-124 A-125 CF₃ H H-125 A-126 CF₃ H H-126 A-127 CF₃ H H-127 A-128 CF₃ H H-128 A-129 CF₃ H H-129 A-130 CF₃ H H-130 A-131 CF₃ H H-131 A-132 CF₃ H H-132 A-133 CF₃ H H-133 A-134 CF₃ H H-134 A-135 CF₃ H H-135 A-136 CF₃ H H-136 A-137 CF₃ H H-137 A-138 CF₃ H H-138 A-139 CF₃ H H-139 A-140 CF₃ H H-140 A-141 CF₃ H H-141 A-142 CF₃ H H-142 A-143 CF₃ H H-143 A-144 CF₃ H H-144 A-145 CF₃ H H-145 A-146 CF₃ H H-146 A-147 CF₃ H H-147 A-148 CF₃ H H-148 A-149 CF₃ H H-149 A-150 CF₃ H H-150 A-151 CF₃ H H-151 A-152 CF₃ H H-152 A-153 CF₃ H H-153 A-154 CF₃ H H-154 A-155 CF₃ H H-155 A-156 CF₃ H H-156 A-157 CF₃ H H-157 A-158 CF₃ H H-158 A-159 CF₃ H H-159 A-160 CF₃ H H-160 A-161 CF₃ H H-161 A-162 CF₃ H H-162 A-163 C₂F₅ H H-1 A-164 C₂F₅ H H-2 A-165 C₂F₅ H H-3 A-166 C₂F₅ H H-4 A-167 C₂F₅ H H-5 A-168 C₂F₅ H H-6 A-169 C₂F₅ H H-7 A-170 C₂F₅ H H-8 A-171 C₂F₅ H H-9 A-172 C₂F₅ H H-10 A-173 C₂F₅ H H-11 A-174 C₂F₅ H H-12 A-175 C₂F₅ H H-13 A-176 C₂F₅ H H-14 A-177 C₂F₅ H H-15 A-178 C₂F₅ H H-16 A-179 C₂F₅ H H-17 A-180 C₂F₅ H H-18 A-181 C₂F₅ H H-19 A-182 C₂F₅ H H-20 A-183 C₂F₅ H H-21 A-184 C₂F₅ H H-22 A-185 C₂F₅ H H-23 A-186 C₂F₅ H H-24 A-187 C₂F₅ H H-25 A-188 C₂F₅ H H-26 A-189 C₂F₅ H H-27 A-190 C₂F₅ H H-28 A-191 C₂F₅ H H-29 A-192 C₂F₅ H H-30 A-193 C₂F₅ H H-31 A-194 C₂F₅ H H-32 A-195 C₂F₅ H H-33 A-196 C₂F₅ H H-34 A-197 C₂F₅ H H-35 A-198 C₂F₅ H H-36 A-199 C₂F₅ H H-37 A-200 C₂F₅ H H-38 A-201 C₂F₅ H H-39 A-202 C₂F₅ H H-40 A-203 C₂F₅ H H-41 A-204 C₂F₅ H H-42 A-205 C₂F₅ H H-43 A-206 C₂F₅ H H-44 A-207 C₂F₅ H H-45 A-208 C₂F₅ H H-46 A-209 C₂F₅ H H-47 A-210 C₂F₅ H H-48 A-211 C₂F₅ H H-49 A-212 C₂F₅ H H-50 A-213 C₂F₅ H H-51 A-214 C₂F₅ H H-52 A-215 C₂F₅ H H-53 A-216 C₂F₅ H H-54 A-217 C₂F₅ H H-55 A-218 C₂F₅ H H-56 A-219 C₂F₅ H H-57 A-220 C₂F₅ H H-58 A-221 C₂F₅ H H-59 A-222 C₂F₅ H H-60 A-223 C₂F₅ H H-61 A-224 C₂F₅ H H-62 A-225 C₂F₅ H H-63 A-226 C₂F₅ H H-64 A-227 C₂F₅ H H-65 A-228 C₂F₅ H H-66 A-229 C₂F₅ H H-67 A-230 C₂F₅ H H-68 A-231 C₂F₅ H H-69 A-232 C₂F₅ H H-70 A-233 C₂F₅ H H-71 A-234 C₂F₅ H H-72 A-235 C₂F₅ H H-73 A-236 C₂F₅ H H-74 A-237 C₂F₅ H H-75 A-238 C₂F₅ H H-76 A-239 C₂F₅ H H-77 A-240 C₂F₅ H H-78 A-241 C₂F₅ H H-79 A-242 C₂F₅ H H-80 A-243 C₂F₅ H H-81 A-244 C₂F₅ H H-82 A-245 C₂F₅ H H-83 A-246 C₂F₅ H H-84 A-247 C₂F₅ H H-85 A-248 C₂F₅ H H-86 A-249 C₂F₅ H H-87 A-250 C₂F₅ H H-88 A-251 C₂F₅ H H-89 A-252 C₂F₅ H H-90 A-253 C₂F₅ H H-91 A-254 C₂F₅ H H-92 A-255 C₂F₅ H H-93 A-256 C₂F₅ H H-94 A-257 C₂F₅ H H-95 A-258 C₂F₅ H H-96 A-259 C₂F₅ H H-97 A-260 C₂F₅ H H-98 A-261 C₂F₅ H H-99 A-262 C₂F₅ H H-100 A-263 C₂F₅ H H-101 A-264 C₂F₅ H H-102 A-265 C₂F₅ H H-103 A-266 C₂F₅ H H-104 A-267 C₂F₅ H H-105 A-268 C₂F₅ H H-106 A-269 C₂F₅ H H-107 A-270 C₂F₅ H H-108 A-271 C₂F₅ H H-109 A-272 C₂F₅ H H-110 A-273 C₂F₅ H H-111 A-274 C₂F₅ H H-112 A-275 C₂F₅ H H-113 A-276 C₂F₅ H H-114 A-277 C₂F₅ H H-115 A-278 C₂F₅ H H-116 A-279 C₂F₅ H H-117 A-280 C₂F₅ H H-118 A-281 C₂F₅ H H-119 A-282 C₂F₅ H H-120 A-283 C₂F₅ H H-121 A-284 C₂F₅ H H-122 A-285 C₂F₅ H H-123 A-286 C₂F₅ H H-124 A-287 C₂F₅ H H-125 A-288 C₂F₅ H H-126 A-289 C₂F₅ H H-127 A-290 C₂F₅ H H-128 A-291 C₂F₅ H H-129 A-292 C₂F₅ H H-130 A-293 C₂F₅ H H-131 A-294 C₂F₅ H H-132 A-295 C₂F₅ H H-133 A-296 C₂F₅ H H-134 A-297 C₂F₅ H H-135 A-298 C₂F₅ H H-136 A-299 C₂F₅ H H-137 A-300 C₂F₅ H H-138 A-301 C₂F₅ H H-139 A-302 C₂F₅ H H-140 A-303 C₂F₅ H H-141 A-304 C₂F₅ H H-142 A-305 C₂F₅ H H-143 A-306 C₂F₅ H H-144 A-307 C₂F₅ H H-145 A-308 C₂F₅ H H-146 A-309 C₂F₅ H H-147 A-310 C₂F₅ H H-148 A-311 C₂F₅ H H-149 A-312 C₂F₅ H H-150 A-313 C₂F₅ H H-151 A-314 C₂F₅ H H-152 A-315 C₂F₅ H H-153 A-316 C₂F₅ H H-154 A-317 C₂F₅ H H-155 A-318 C₂F₅ H H-156 A-319 C₂F₅ H H-157 A-320 C₂F₅ H H-158 A-321 C₂F₅ H H-159 A-322 C₂F₅ H H-160 A-323 C₂F₅ H H-161 A-324 C₂F₅ H H-162 A-325 CF(CF₃)₂ H H-1 A-326 CF(CF₃)₂ H H-2 A-327 CF(CF₃)₂ H H-3 A-328 CF(CF₃)₂ H H-4 A-329 CF(CF₃)₂ H H-5 A-330 CF(CF₃)₂ H H-6 A-331 CF(CF₃)₂ H H-7 A-332 CF(CF₃)₂ H H-8 A-333 CF(CF₃)₂ H H-9 A-334 CF(CF₃)₂ H H-10 A-335 CF(CF₃)₂ H H-11 A-336 CF(CF₃)₂ H H-12 A-337 CF(CF₃)₂ H H-13 A-338 CF(CF₃)₂ H H-14 A-339 CF(CF₃)₂ H H-15 A-340 CF(CF₃)₂ H H-16 A-341 CF(CF₃)₂ H H-17 A-342 CF(CF₃)₂ H H-18 A-343 CF(CF₃)₂ H H-19 A-344 CF(CF₃)₂ H H-20 A-345 CF(CF₃)₂ H H-21 A-346 CF(CF₃)₂ H H-22 A-347 CF(CF₃)₂ H H-23 A-348 CF(CF₃)₂ H H-24 A-349 CF(CF₃)₂ H H-25 A-350 CF(CF₃)₂ H H-26 A-351 CF(CF₃)₂ H H-27 A-352 CF(CF₃)₂ H H-28 A-353 CF(CF₃)₂ H H-29 A-354 CF(CF₃)₂ H H-30 A-355 CF(CF₃)₂ H H-31 A-356 CF(CF₃)₂ H H-32 A-357 CF(CF₃)₂ H H-33 A-358 CF(CF₃)₂ H H-34 A-359 CF(CF₃)₂ H H-35 A-360 CF(CF₃)₂ H H-36 A-361 CF(CF₃)₂ H H-37 A-362 CF(CF₃)₂ H H-38 A-363 CF(CF₃)₂ H H-39 A-364 CF(CF₃)₂ H H-40 A-365 CF(CF₃)₂ H H-41 A-366 CF(CF₃)₂ H H-42 A-367 CF(CF₃)₂ H H-43 A-368 CF(CF₃)₂ H H-44 A-369 CF(CF₃)₂ H H-45 A-370 CF(CF₃)₂ H H-46 A-371 CF(CF₃)₂ H H-47 A-372 CF(CF₃)₂ H H-48 A-373 CF(CF₃)₂ H H-49 A-374 CF(CF₃)₂ H H-50 A-375 CF(CF₃)₂ H H-51 A-376 CF(CF₃)₂ H H-52 A-377 CF(CF₃)₂ H H-53 A-378 CF(CF₃)₂ H H-54 A-379 CF(CF₃)₂ H H-55 A-380 CF(CF₃)₂ H H-56 A-381 CF(CF₃)₂ H H-57 A-382 CF(CF₃)₂ H H-58 A-383 CF(CF₃)₂ H H-59 A-384 CF(CF₃)₂ H H-60 A-385 CF(CF₃)₂ H H-61 A-386 CF(CF₃)₂ H H-62 A-387 CF(CF₃)₂ H H-63 A-388 CF(CF₃)₂ H H-64 A-389 CF(CF₃)₂ H H-65 A-390 CF(CF₃)₂ H H-66 A-391 CF(CF₃)₂ H H-67 A-392 CF(CF₃)₂ H H-68 A-393 CF(CF₃)₂ H H-69 A-394 CF(CF₃)₂ H H-70 A-395 CF(CF₃)₂ H H-71 A-396 CF(CF₃)₂ H H-72 A-397 CF(CF₃)₂ H H-73 A-398 CF(CF₃)₂ H H-74 A-399 CF(CF₃)₂ H H-75 A-400 CF(CF₃)₂ H H-76 A-401 CF(CF₃)₂ H H-77 A-402 CF(CF₃)₂ H H-78 A-403 CF(CF₃)₂ H H-79 A-404 CF(CF₃)₂ H H-80 A-405 CF(CF₃)₂ H H-81 A-406 CF(CF₃)₂ H H-82 A-407 CF(CF₃)₂ H H-83 A-408 CF(CF₃)₂ H H-84 A-409 CF(CF₃)₂ H H-85 A-410 CF(CF₃)₂ H H-86 A-411 CF(CF₃)₂ H H-87 A-412 CF(CF₃)₂ H H-88 A-413 CF(CF₃)₂ H H-89 A-414 CF(CF₃)₂ H H-90 A-415 CF(CF₃)₂ H H-91 A-416 CF(CF₃)₂ H H-92 A-417 CF(CF₃)₂ H H-93 A-418 CF(CF₃)₂ H H-94 A-419 CF(CF₃)₂ H H-95 A-420 CF(CF₃)₂ H H-96 A-421 CF(CF₃)₂ H H-97 A-422 CF(CF₃)₂ H H-98 A-423 CF(CF₃)₂ H H-99 A-424 CF(CF₃)₂ H H-100 A-425 CF(CF₃)₂ H H-101 A-426 CF(CF₃)₂ H H-102 A-427 CF(CF₃)₂ H H-103 A-428 CF(CF₃)₂ H H-104 A-429 CF(CF₃)₂ H H-105 A-430 CF(CF₃)₂ H H-106 A-431 CF(CF₃)₂ H H-107 A-432 CF(CF₃)₂ H H-108 A-433 CF(CF₃)₂ H H-109 A-434 CF(CF₃)₂ H H-110 A-435 CF(CF₃)₂ H H-111 A-436 CF(CF₃)₂ H H-112 A-437 CF(CF₃)₂ H H-113 A-438 CF(CF₃)₂ H H-114 A-439 CF(CF₃)₂ H H-115 A-440 CF(CF₃)₂ H H-116 A-441 CF(CF₃)₂ H H-117 A-442 CF(CF₃)₂ H H-118 A-443 CF(CF₃)₂ H H-119 A-444 CF(CF₃)₂ H H-120 A-445 CF(CF₃)₂ H H-121 A-446 CF(CF₃)₂ H H-122 A-447 CF(CF₃)₂ H H-123 A-448 CF(CF₃)₂ H H-124 A-449 CF(CF₃)₂ H H-125 A-450 CF(CF₃)₂ H H-126 A-451 CF(CF₃)₂ H H-127 A-452 CF(CF₃)₂ H H-128 A-453 CF(CF₃)₂ H H-129 A-454 CF(CF₃)₂ H H-130 A-455 CF(CF₃)₂ H H-131 A-456 CF(CF₃)₂ H H-132 A-457 CF(CF₃)₂ H H-133 A-458 CF(CF₃)₂ H H-134 A-459 CF(CF₃)₂ H H-135 A-460 CF(CF₃)₂ H H-136 A-461 CF(CF₃)₂ H H-137 A-462 CF(CF₃)₂ H H-138 A-463 CF(CF₃)₂ H H-139 A-464 CF(CF₃)₂ H H-140 A-465 CF(CF₃)₂ H H-141 A-466 CF(CF₃)₂ H H-142 A-467 CF(CF₃)₂ H H-143 A-468 CF(CF₃)₂ H H-144 A-469 CF(CF₃)₂ H H-145 A-470 CF(CF₃)₂ H H-146 A-471 CF(CF₃)₂ H H-147 A-472 CF(CF₃)₂ H H-148 A-473 CF(CF₃)₂ H H-149 A-474 CF(CF₃)₂ H H-150 A-475 CF(CF₃)₂ H H-151 A-476 CF(CF₃)₂ H H-152 A-477 CF(CF₃)₂ H H-153 A-478 CF(CF₃)₂ H H-154 A-479 CF(CF₃)₂ H H-155 A-480 CF(CF₃)₂ H H-156 A-481 CF(CF₃)₂ H H-157 A-482 CF(CF₃)₂ H H-158 A-483 CF(CF₃)₂ H H-159 A-484 CF(CF₃)₂ H H-160 A-485 CF(CF₃)₂ H H-161 A-486 CF(CF₃)₂ H H-162 A-487 SCF₃ H H-1 A-488 SCF₃ H H-2 A-489 SCF₃ H H-3 A-490 SCF₃ H H-4 A-491 SCF₃ H H-5 A-492 SCF₃ H H-6 A-493 SCF₃ H H-7 A-494 SCF₃ H H-8 A-495 SCF₃ H H-9 A-496 SCF₃ H H-10 A-497 SCF₃ H H-11 A-498 SCF₃ H H-12 A-499 SCF₃ H H-13 A-500 SCF₃ H H-14 A-501 SCF₃ H H-15 A-502 SCF₃ H H-16 A-503 SCF₃ H H-17 A-504 SCF₃ H H-18 A-505 SCF₃ H H-19 A-506 SCF₃ H H-20 A-507 SCF₃ H H-21 A-508 SCF₃ H H-22 A-509 SCF₃ H H-23 A-510 SCF₃ H H-24 A-511 SCF₃ H H-25 A-512 SCF₃ H H-26 A-513 SCF₃ H H-27 A-514 SCF₃ H H-28 A-515 SCF₃ H H-29 A-516 SCF₃ H H-30 A-517 SCF₃ H H-31 A-518 SCF₃ H H-32 A-519 SCF₃ H H-33 A-520 SCF₃ H H-34 A-521 SCF₃ H H-35 A-522 SCF₃ H H-36 A-523 SCF₃ H H-37 A-524 SCF₃ H H-38 A-525 SCF₃ H H-39 A-526 SCF₃ H H-40 A-527 SCF₃ H H-41 A-528 SCF₃ H H-42 A-529 SCF₃ H H-43 A-530 SCF₃ H H-44 A-531 SCF₃ H H-45 A-532 SCF₃ H H-46 A-533 SCF₃ H H-47 A-534 SCF₃ H H-48 A-535 SCF₃ H H-49 A-536 SCF₃ H H-50 A-537 SCF₃ H H-51 A-538 SCF₃ H H-52 A-539 SCF₃ H H-53 A-540 SCF₃ H H-54 A-541 SCF₃ H H-55 A-542 SCF₃ H H-56 A-543 SCF₃ H H-57 A-544 SCF₃ H H-58 A-545 SCF₃ H H-59 A-546 SCF₃ H H-60 A-547 SCF₃ H H-61 A-548 SCF₃ H H-62 A-549 SCF₃ H H-63 A-550 SCF₃ H H-64 A-551 SCF₃ H H-65 A-552 SCF₃ H H-66 A-553 SCF₃ H H-67 A-554 SCF₃ H H-68 A-555 SCF₃ H H-69 A-556 SCF₃ H H-70 A-557 SCF₃ H H-71 A-558 SCF₃ H H-72 A-559 SCF₃ H H-73 A-560 SCF₃ H H-74 A-561 SCF₃ H H-75 A-562 SCF₃ H H-76 A-563 SCF₃ H H-77 A-564 SCF₃ H H-78 A-565 SCF₃ H H-79 A-566 SCF₃ H H-80 A-567 SCF₃ H H-81 A-568 SCF₃ H H-82 A-569 SCF₃ H H-83 A-570 SCF₃ H H-84 A-571 SCF₃ H H-85 A-572 SCF₃ H H-86 A-573 SCF₃ H H-87 A-574 SCF₃ H H-88 A-575 SCF₃ H H-89 A-576 SCF₃ H H-90 A-577 SCF₃ H H-91 A-578 SCF₃ H H-92 A-579 SCF₃ H H-93 A-580 SCF₃ H H-94 A-581 SCF₃ H H-95 A-582 SCF₃ H H-96 A-583 SCF₃ H H-97 A-584 SCF₃ H H-98 A-585 SCF₃ H H-99 A-586 SCF₃ H H-100 A-587 SCF₃ H H-101 A-588 SCF₃ H H-102 A-589 SCF₃ H H-103 A-590 SCF₃ H H-104 A-591 SCF₃ H H-105 A-592 SCF₃ H H-106 A-593 SCF₃ H H-107 A-594 SCF₃ H H-108 A-595 SCF₃ H H-109 A-596 SCF₃ H H-110 A-597 SCF₃ H H-111 A-598 SCF₃ H H-112 A-599 SCF₃ H H-113 A-600 SCF₃ H H-114 A-601 SCF₃ H H-115 A-602 SCF₃ H H-116 A-603 SCF₃ H H-117 A-604 SCF₃ H H-118 A-605 SCF₃ H H-119 A-606 SCF₃ H H-120 A-607 SCF₃ H H-121 A-608 SCF₃ H H-122 A-609 SCF₃ H H-123 A-610 SCF₃ H H-124 A-611 SCF₃ H H-125 A-612 SCF₃ H H-126 A-613 SCF₃ H H-127 A-614 SCF₃ H H-128 A-615 SCF₃ H H-129 A-616 SCF₃ H H-130 A-617 SCF₃ H H-131 A-618 SCF₃ H H-132 A-619 SCF₃ H H-133 A-620 SCF₃ H H-134 A-621 SCF₃ H H-135 A-622 SCF₃ H H-136 A-623 SCF₃ H H-137 A-624 SCF₃ H H-138 A-625 SCF₃ H H-139 A-626 SCF₃ H H-140 A-627 SCF₃ H H-141 A-628 SCF₃ H H-142 A-629 SCF₃ H H-143 A-630 SCF₃ H H-144 A-631 SCF₃ H H-145 A-632 SCF₃ H H-146 A-633 SCF₃ H H-147 A-634 SCF₃ H H-148 A-635 SCF₃ H H-149 A-636 SCF₃ H H-150 A-637 SCF₃ H H-151 A-638 SCF₃ H H-152 A-639 SCF₃ H H-153 A-640 SCF₃ H H-154 A-641 SCF₃ H H-155 A-642 SCF₃ H H-156 A-643 SCF₃ H H-157 A-644 SCF₃ H H-158 A-645 SCF₃ H H-159 A-646 SCF₃ H H-160 A-647 SCF₃ H H-161 A-648 SCF₃ H H-162 A-649 OCF₃ H H-1 A-650 OCF₃ H H-2 A-651 OCF₃ H H-3 A-652 OCF₃ H H-4 A-653 OCF₃ H H-5 A-654 OCF₃ H H-6 A-655 OCF₃ H H-7 A-656 OCF₃ H H-8 A-657 OCF₃ H H-9 A-658 OCF₃ H H-10 A-659 OCF₃ H H-11 A-660 OCF₃ H H-12 A-661 OCF₃ H H-13 A-662 OCF₃ H H-14 A-663 OCF₃ H H-15 A-664 OCF₃ H H-16 A-665 OCF₃ H H-17 A-666 OCF₃ H H-18 A-667 OCF₃ H H-19 A-668 OCF₃ H H-20 A-669 OCF₃ H H-21 A-670 OCF₃ H H-22 A-671 OCF₃ H H-23 A-672 OCF₃ H H-24 A-673 OCF₃ H H-25 A-674 OCF₃ H H-26 A-675 OCF₃ H H-27 A-676 OCF₃ H H-28 A-677 OCF₃ H H-29 A-678 OCF₃ H H-30 A-679 OCF₃ H H-31 A-680 OCF₃ H H-32 A-681 OCF₃ H H-33 A-682 OCF₃ H H-34 A-683 OCF₃ H H-35 A-684 OCF₃ H H-36 A-685 OCF₃ H H-37 A-686 OCF₃ H H-38 A-687 OCF₃ H H-39 A-688 OCF₃ H H-40 A-689 OCF₃ H H-41 A-690 OCF₃ H H-42 A-691 OCF₃ H H-43 A-692 OCF₃ H H-44 A-693 OCF₃ H H-45 A-694 OCF₃ H H-46 A-695 OCF₃ H H-47 A-696 OCF₃ H H-48 A-697 OCF₃ H H-49 A-698 OCF₃ H H-50 A-699 OCF₃ H H-51 A-700 OCF₃ H H-52 A-701 OCF₃ H H-53 A-702 OCF₃ H H-54 A-703 OCF₃ H H-55 A-704 OCF₃ H H-56 A-705 OCF₃ H H-57 A-706 OCF₃ H H-58 A-707 OCF₃ H H-59 A-708 OCF₃ H H-60 A-709 OCF₃ H H-61 A-710 OCF₃ H H-62 A-711 OCF₃ H H-63 A-712 OCF₃ H H-64 A-713 OCF₃ H H-65 A-714 OCF₃ H H-66 A-715 OCF₃ H H-67 A-716 OCF₃ H H-68 A-717 OCF₃ H H-69 A-718 OCF₃ H H-70 A-719 OCF₃ H H-71 A-720 OCF₃ H H-72 A-721 OCF₃ H H-73 A-722 OCF₃ H H-74 A-723 OCF₃ H H-75 A-724 OCF₃ H H-76 A-725 OCF₃ H H-77 A-726 OCF₃ H H-78 A-727 OCF₃ H H-79 A-728 OCF₃ H H-80 A-729 OCF₃ H H-81 A-730 OCF₃ H H-82 A-731 OCF₃ H H-83 A-732 OCF₃ H H-84 A-733 OCF₃ H H-85 A-734 OCF₃ H H-86 A-735 OCF₃ H H-87 A-736 OCF₃ H H-88 A-737 OCF₃ H H-89 A-738 OCF₃ H H-90 A-739 OCF₃ H H-91 A-740 OCF₃ H H-92 A-741 OCF₃ H H-93 A-742 OCF₃ H H-94 A-743 OCF₃ H H-95 A-744 OCF₃ H H-96 A-745 OCF₃ H H-97 A-746 OCF₃ H H-98 A-747 OCF₃ H H-99 A-748 OCF₃ H H-100 A-749 OCF₃ H H-101 A-750 OCF₃ H H-102 A-751 OCF₃ H H-103 A-752 OCF₃ H H-104 A-753 OCF₃ H H-105 A-754 OCF₃ H H-106 A-755 OCF₃ H H-107 A-756 OCF₃ H H-108 A-757 OCF₃ H H-109 A-758 OCF₃ H H-110 A-759 OCF₃ H H-111 A-760 OCF₃ H H-112 A-761 OCF₃ H H-113 A-762 OCF₃ H H-114 A-763 OCF₃ H H-115 A-764 OCF₃ H H-116 A-765 OCF₃ H H-117 A-766 OCF₃ H H-118 A-767 OCF₃ H H-119 A-768 OCF₃ H H-120 A-769 OCF₃ H H-121 A-770 OCF₃ H H-122 A-771 OCF₃ H H-123 A-772 OCF₃ H H-124 A-773 OCF₃ H H-125 A-774 OCF₃ H H-126 A-775 OCF₃ H H-127 A-776 OCF₃ H H-128 A-777 OCF₃ H H-129 A-778 OCF₃ H H-130 A-779 OCF₃ H H-131 A-780 OCF₃ H H-132 A-781 OCF₃ H H-133 A-782 OCF₃ H H-134 A-783 OCF₃ H H-135 A-784 OCF₃ H H-136 A-785 OCF₃ H H-137 A-786 OCF₃ H H-138 A-787 OCF₃ H H-139 A-788 OCF₃ H H-140 A-789 OCF₃ H H-141 A-790 OCF₃ H H-142 A-791 OCF₃ H H-143 A-792 OCF₃ H H-144 A-793 OCF₃ H H-145 A-794 OCF₃ H H-146 A-795 OCF₃ H H-147 A-796 OCF₃ H H-148 A-797 OCF₃ H H-149 A-798 OCF₃ H H-150 A-799 OCF₃ H H-151 A-800 OCF₃ H H-152 A-801 OCF₃ H H-153 A-802 OCF₃ H H-154 A-803 OCF₃ H H-155 A-804 OCF₃ H H-156 A-805 OCF₃ H H-157 A-806 OCF₃ H H-158 A-807 OCF₃ H H-159 A-808 OCF₃ H H-160 A-809 OCF₃ H H-161 A-810 OCF₃ H H-162 A-811 OCHF₂ H H-1 A-812 OCHF₂ H H-2 A-813 OCHF₂ H H-3 A-814 OCHF₂ H H-4 A-815 OCHF₂ H H-5 A-816 OCHF₂ H H-6 A-817 OCHF₂ H H-7 A-818 OCHF₂ H H-8 A-819 OCHF₂ H H-9 A-820 OCHF₂ H H-10 A-821 OCHF₂ H H-11 A-822 OCHF₂ H H-12 A-823 OCHF₂ H H-13 A-824 OCHF₂ H H-14 A-825 OCHF₂ H H-15 A-826 OCHF₂ H H-16 A-827 OCHF₂ H H-17 A-828 OCHF₂ H H-18 A-829 OCHF₂ H H-19 A-830 OCHF₂ H H-20 A-831 OCHF₂ H H-21 A-832 OCHF₂ H H-22 A-833 OCHF₂ H H-23 A-834 OCHF₂ H H-24 A-835 OCHF₂ H H-25 A-836 OCHF₂ H H-26 A-837 OCHF₂ H H-27 A-838 OCHF₂ H H-28 A-839 OCHF₂ H H-29 A-840 OCHF₂ H H-30 A-841 OCHF₂ H H-31 A-842 OCHF₂ H H-32 A-843 OCHF₂ H H-33 A-844 OCHF₂ H H-34 A-845 OCHF₂ H H-35 A-846 OCHF₂ H H-36 A-847 OCHF₂ H H-37 A-848 OCHF₂ H H-38 A-849 OCHF₂ H H-39 A-850 OCHF₂ H H-40 A-851 OCHF₂ H H-41 A-852 OCHF₂ H H-42 A-853 OCHF₂ H H-43 A-854 OCHF₂ H H-44 A-855 OCHF₂ H H-45 A-856 OCHF₂ H H-46 A-857 OCHF₂ H H-47 A-858 OCHF₂ H H-48 A-859 OCHF₂ H H-49 A-860 OCHF₂ H H-50 A-861 OCHF₂ H H-51 A-862 OCHF₂ H H-52 A-863 OCHF₂ H H-53 A-864 OCHF₂ H H-54 A-865 OCHF₂ H H-55 A-866 OCHF₂ H H-56 A-867 OCHF₂ H H-57 A-868 OCHF₂ H H-58 A-869 OCHF₂ H H-59 A-870 OCHF₂ H H-60 A-871 OCHF₂ H H-61 A-872 OCHF₂ H H-62 A-873 OCHF₂ H H-63 A-874 OCHF₂ H H-64 A-875 OCHF₂ H H-65 A-876 OCHF₂ H H-66 A-877 OCHF₂ H H-67 A-878 OCHF₂ H H-68 A-879 OCHF₂ H H-69 A-880 OCHF₂ H H-70 A-881 OCHF₂ H H-71 A-882 OCHF₂ H H-72 A-883 OCHF₂ H H-73 A-884 OCHF₂ H H-74 A-885 OCHF₂ H H-75 A-886 OCHF₂ H H-76 A-887 OCHF₂ H H-77 A-888 OCHF₂ H H-78 A-889 OCHF₂ H H-79 A-890 OCHF₂ H H-80 A-891 OCHF₂ H H-81 A-892 OCHF₂ H H-82 A-893 OCHF₂ H H-83 A-894 OCHF₂ H H-84 A-895 OCHF₂ H H-85 A-896 OCHF₂ H H-86 A-897 OCHF₂ H H-87 A-898 OCHF₂ H H-88 A-899 OCHF₂ H H-89 A-900 OCHF₂ H H-90 A-901 OCHF₂ H H-91 A-902 OCHF₂ H H-92 A-903 OCHF₂ H H-93 A-904 OCHF₂ H H-94 A-905 OCHF₂ H H-95 A-906 OCHF₂ H H-96 A-907 OCHF₂ H H-97 A-908 OCHF₂ H H-98 A-909 OCHF₂ H H-99 A-910 OCHF₂ H H-100 A-911 OCHF₂ H H-101 A-912 OCHF₂ H H-102 A-913 OCHF₂ H H-103 A-914 OCHF₂ H H-104 A-915 OCHF₂ H H-105 A-916 OCHF₂ H H-106 A-917 OCHF₂ H H-107 A-918 OCHF₂ H H-108 A-919 OCHF₂ H H-109 A-920 OCHF₂ H H-110 A-921 OCHF₂ H H-111 A-922 OCHF₂ H H-112 A-923 OCHF₂ H H-113 A-924 OCHF₂ H H-114 A-925 OCHF₂ H H-115 A-926 OCHF₂ H H-116 A-927 OCHF₂ H H-117 A-928 OCHF₂ H H-118 A-929 OCHF₂ H H-119 A-930 OCHF₂ H H-120 A-931 OCHF₂ H H-121 A-932 OCHF₂ H H-122 A-933 OCHF₂ H H-123 A-934 OCHF₂ H H-124 A-935 OCHF₂ H H-125 A-936 OCHF₂ H H-126 A-937 OCHF₂ H H-127 A-938 OCHF₂ H H-128 A-939 OCHF₂ H H-129 A-940 OCHF₂ H H-130 A-941 OCHF₂ H H-131 A-942 OCHF₂ H H-132 A-943 OCHF₂ H H-133 A-944 OCHF₂ H H-134 A-945 OCHF₂ H H-135 A-946 OCHF₂ H H-136 A-947 OCHF₂ H H-137 A-948 OCHF₂ H H-138 A-949 OCHF₂ H H-139 A-950 OCHF₂ H H-140 A-951 OCHF₂ H H-141 A-952 OCHF₂ H H-142 A-953 OCHF₂ H H-143 A-954 OCHF₂ H H-144 A-955 OCHF₂ H H-145 A-956 OCHF₂ H H-146 A-957 OCHF₂ H H-147 A-958 OCHF₂ H H-148 A-959 OCHF₂ H H-149 A-960 OCHF₂ H H-150 A-961 OCHF₂ H H-151 A-962 OCHF₂ H H-152 A-963 OCHF₂ H H-153 A-964 OCHF₂ H H-154 A-965 OCHF₂ H H-155 A-966 OCHF₂ H H-156 A-967 OCHF₂ H H-157 A-968 OCHF₂ H H-158 A-969 OCHF₂ H H-159 A-970 OCHF₂ H H-160 A-971 OCHF₂ H H-161 A-972 OCHF₂ H H-162 A-973 S(═O)CF₃ H H-1 A-974 S(═O)CF₃ H H-2 A-975 S(═O)CF₃ H H-3 A-976 S(═O)CF₃ H H-4 A-977 S(═O)CF₃ H H-5 A-978 S(═O)CF₃ H H-6 A-979 S(═O)CF₃ H H-7 A-980 S(═O)CF₃ H H-8 A-981 S(═O)CF₃ H H-9 A-982 S(═O)CF₃ H H-10 A-983 S(═O)CF₃ H H-11 A-984 S(═O)CF₃ H H-12 A-985 S(═O)CF₃ H H-13 A-986 S(═O)CF₃ H H-14 A-987 S(═O)CF₃ H H-15 A-988 S(═O)CF₃ H H-16 A-989 S(═O)CF₃ H H-17 A-990 S(═O)CF₃ H H-18 A-991 S(═O)CF₃ H H-19 A-992 S(═O)CF₃ H H-20 A-993 S(═O)CF₃ H H-21 A-994 S(═O)CF₃ H H-22 A-995 S(═O)CF₃ H H-23 A-996 S(═O)CF₃ H H-24 A-997 S(═O)CF₃ H H-25 A-998 S(═O)CF₃ H H-26 A-999 S(═O)CF₃ H H-27 A-1000 S(═O)CF₃ H H-28 A-1001 S(═O)CF₃ H H-29 A-1002 S(═O)CF₃ H H-30 A-1003 S(═O)CF₃ H H-31 A-1004 S(═O)CF₃ H H-32 A-1005 S(═O)CF₃ H H-33 A-1006 S(═O)CF₃ H H-34 A-1007 S(═O)CF₃ H H-35 A-1008 S(═O)CF₃ H H-36 A-1009 S(═O)CF₃ H H-37 A-1010 S(═O)CF₃ H H-38 A-1011 S(═O)CF₃ H H-39 A-1012 S(═O)CF₃ H H-40 A-1013 S(═O)CF₃ H H-41 A-1014 S(═O)CF₃ H H-42 A-1015 S(═O)CF₃ H H-43 A-1016 S(═O)CF₃ H H-44 A-1017 S(═O)CF₃ H H-45 A-1018 S(═O)CF₃ H H-46 A-1019 S(═O)CF₃ H H-47 A-1020 S(═O)CF₃ H H-48 A-1021 S(═O)CF₃ H H-49 A-1022 S(═O)CF₃ H H-50 A-1023 S(═O)CF₃ H H-51 A-1024 S(═O)CF₃ H H-52 A-1025 S(═O)CF₃ H H-53 A-1026 S(═O)CF₃ H H-54 A-1027 S(═O)CF₃ H H-55 A-1028 S(═O)CF₃ H H-56 A-1029 S(═O)CF₃ H H-57 A-1030 S(═O)CF₃ H H-58 A-1031 S(═O)CF₃ H H-59 A-1032 S(═O)CF₃ H H-60 A-1033 S(═O)CF₃ H H-61 A-1034 S(═O)CF₃ H H-62 A-1035 S(═O)CF₃ H H-63 A-1036 S(═O)CF₃ H H-64 A-1037 S(═O)CF₃ H H-65 A-1038 S(═O)CF₃ H H-66 A-1039 S(═O)CF₃ H H-67 A-1040 S(═O)CF₃ H H-68 A-1041 S(═O)CF₃ H H-69 A-1042 S(═O)CF₃ H H-70 A-1043 S(═O)CF₃ H H-71 A-1044 S(═O)CF₃ H H-72 A-1045 S(═O)CF₃ H H-73 A-1046 S(═O)CF₃ H H-74 A-1047 S(═O)CF₃ H H-75 A-1048 S(═O)CF₃ H H-76 A-1049 S(═O)CF₃ H H-77 A-1050 S(═O)CF₃ H H-78 A-1051 S(═O)CF₃ H H-79 A-1052 S(═O)CF₃ H H-80 A-1053 S(═O)CF₃ H H-81 A-1054 S(═O)CF₃ H H-82 A-1055 S(═O)CF₃ H H-83 A-1056 S(═O)CF₃ H H-84 A-1057 S(═O)CF₃ H H-85 A-1058 S(═O)CF₃ H H-86 A-1059 S(═O)CF₃ H H-87 A-1060 S(═O)CF₃ H H-88 A-1061 S(═O)CF₃ H H-89 A-1062 S(═O)CF₃ H H-90 A-1063 S(═O)CF₃ H H-91 A-1064 S(═O)CF₃ H H-92 A-1065 S(═O)CF₃ H H-93 A-1066 S(═O)CF₃ H H-94 A-1067 S(═O)CF₃ H H-95 A-1068 S(═O)CF₃ H H-96 A-1069 S(═O)CF₃ H H-97 A-1070 S(═O)CF₃ H H-98 A-1071 S(═O)CF₃ H H-99 A-1072 S(═O)CF₃ H H-100 A-1073 S(═O)CF₃ H H-101 A-1074 S(═O)CF₃ H H-102 A-1075 S(═O)CF₃ H H-103 A-1076 S(═O)CF₃ H H-104 A-1077 S(═O)CF₃ H H-105 A-1078 S(═O)CF₃ H H-106 A-1079 S(═O)CF₃ H H-107 A-1080 S(═O)CF₃ H H-108 A-1081 S(═O)CF₃ H H-109 A-1082 S(═O)CF₃ H H-110 A-1083 S(═O)CF₃ H H-111 A-1084 S(═O)CF₃ H H-112 A-1085 S(═O)CF₃ H H-113 A-1086 S(═O)CF₃ H H-114 A-1087 S(═O)CF₃ H H-115 A-1088 S(═O)CF₃ H H-116 A-1089 S(═O)CF₃ H H-117 A-1090 S(═O)CF₃ H H-118 A-1091 S(═O)CF₃ H H-119 A-1092 S(═O)CF₃ H H-120 A-1093 S(═O)CF₃ H H-121 A-1094 S(═O)CF₃ H H-122 A-1095 S(═O)CF₃ H H-123 A-1096 S(═O)CF₃ H H-124 A-1097 S(═O)CF₃ H H-125 A-1098 S(═O)CF₃ H H-126 A-1099 S(═O)CF₃ H H-127 A-1100 S(═O)CF₃ H H-128 A-1101 S(═O)CF₃ H H-129 A-1102 S(═O)CF₃ H H-130 A-1103 S(═O)CF₃ H H-131 A-1104 S(═O)CF₃ H H-132 A-1105 S(═O)CF₃ H H-133 A-1106 S(═O)CF₃ H H-134 A-1107 S(═O)CF₃ H H-135 A-1108 S(═O)CF₃ H H-136 A-1109 S(═O)CF₃ H H-137 A-1110 S(═O)CF₃ H H-138 A-1111 S(═O)CF₃ H H-139 A-1112 S(═O)CF₃ H H-140 A-1113 S(═O)CF₃ H H-141 A-1114 S(═O)CF₃ H H-142 A-1115 S(═O)CF₃ H H-143 A-1116 S(═O)CF₃ H H-144 A-1117 S(═O)CF₃ H H-145 A-1118 S(═O)CF₃ H H-146 A-1119 S(═O)CF₃ H H-147 A-1120 S(═O)CF₃ H H-148 A-1121 S(═O)CF₃ H H-149 A-1122 S(═O)CF₃ H H-150 A-1123 S(═O)CF₃ H H-151 A-1124 S(═O)CF₃ H H-152 A-1125 S(═O)CF₃ H H-153 A-1126 S(═O)CF₃ H H-154 A-1127 S(═O)CF₃ H H-155 A-1128 S(═O)CF₃ H H-156 A-1129 S(═O)CF₃ H H-157 A-1130 S(═O)CF₃ H H-158 A-1131 S(═O)CF₃ H H-159 A-1132 S(═O)CF₃ H H-160 A-1133 S(═O)CF₃ H H-161 A-1134 S(═O)CF₃ H H-162 A-1135 S(═O)₂CF₃ H H-1 A-1136 S(═O)₂CF₃ H H-2 A-1137 S(═O)₂CF₃ H H-3 A-1138 S(═O)₂CF₃ H H-4 A-1139 S(═O)₂CF₃ H H-5 A-1140 S(═O)₂CF₃ H H-6 A-1141 S(═O)₂CF₃ H H-7 A-1142 S(═O)₂CF₃ H H-8 A-1143 S(═O)₂CF₃ H H-9 A-1144 S(═O)₂CF₃ H H-10 A-1145 S(═O)₂CF₃ H H-11 A-1146 S(═O)₂CF₃ H H-12 A-1147 S(═O)₂CF₃ H H-13 A-1148 S(═O)₂CF₃ H H-14 A-1149 S(═O)₂CF₃ H H-15 A-1150 S(═O)₂CF₃ H H-16 A-1151 S(═O)₂CF₃ H H-17 A-1152 S(═O)₂CF₃ H H-18 A-1153 S(═O)₂CF₃ H H-19 A-1154 S(═O)₂CF₃ H H-20 A-1155 S(═O)₂CF₃ H H-21 A-1156 S(═O)₂CF₃ H H-22 A-1157 S(═O)₂CF₃ H H-23 A-1158 S(═O)₂CF₃ H H-24 A-1159 S(═O)₂CF₃ H H-25 A-1160 S(═O)₂CF₃ H H-26 A-1161 S(═O)₂CF₃ H H-27 A-1162 S(═O)₂CF₃ H H-28 A-1163 S(═O)₂CF₃ H H-29 A-1164 S(═O)₂CF₃ H H-30 A-1165 S(═O)₂CF₃ H H-31 A-1166 S(═O)₂CF₃ H H-32 A-1167 S(═O)₂CF₃ H H-33 A-1168 S(═O)₂CF₃ H H-34 A-1169 S(═O)₂CF₃ H H-35 A-1170 S(═O)₂CF₃ H H-36 A-1171 S(═O)₂CF₃ H H-37 A-1172 S(═O)₂CF₃ H H-38 A-1173 S(═O)₂CF₃ H H-39 A-1174 S(═O)₂CF₃ H H-40 A-1175 S(═O)₂CF₃ H H-41 A-1176 S(═O)₂CF₃ H H-42 A-1177 S(═O)₂CF₃ H H-43 A-1178 S(═O)₂CF₃ H H-44 A-1179 S(═O)₂CF₃ H H-45 A-1180 S(═O)₂CF₃ H H-46 A-1181 S(═O)₂CF₃ H H-47 A-1182 S(═O)₂CF₃ H H-48 A-1183 S(═O)₂CF₃ H H-49 A-1184 S(═O)₂CF₃ H H-50 A-1185 S(═O)₂CF₃ H H-51 A-1186 S(═O)₂CF₃ H H-52 A-1187 S(═O)₂CF₃ H H-53 A-1188 S(═O)₂CF₃ H H-54 A-1189 S(═O)₂CF₃ H H-55 A-1190 S(═O)₂CF₃ H H-56 A-1191 S(═O)₂CF₃ H H-57 A-1192 S(═O)₂CF₃ H H-58 A-1193 S(═O)₂CF₃ H H-59 A-1194 S(═O)₂CF₃ H H-60 A-1195 S(═O)₂CF₃ H H-61 A-1196 S(═O)₂CF₃ H H-62 A-1197 S(═O)₂CF₃ H H-63 A-1198 S(═O)₂CF₃ H H-64 A-1199 S(═O)₂CF₃ H H-65 A-1200 S(═O)₂CF₃ H H-66 A-1201 S(═O)₂CF₃ H H-67 A-1202 S(═O)₂CF₃ H H-68 A-1203 S(═O)₂CF₃ H H-69 A-1204 S(═O)₂CF₃ H H-70 A-1205 S(═O)₂CF₃ H H-71 A-1206 S(═O)₂CF₃ H H-72 A-1207 S(═O)₂CF₃ H H-73 A-1208 S(═O)₂CF₃ H H-74 A-1209 S(═O)₂CF₃ H H-75 A-1210 S(═O)₂CF₃ H H-76 A-1211 S(═O)₂CF₃ H H-77 A-1212 S(═O)₂CF₃ H H-78 A-1213 S(═O)₂CF₃ H H-79 A-1214 S(═O)₂CF₃ H H-80 A-1215 S(═O)₂CF₃ H H-81 A-1216 S(═O)₂CF₃ H H-82 A-1217 S(═O)₂CF₃ H H-83 A-1218 S(═O)₂CF₃ H H-84 A-1219 S(═O)₂CF₃ H H-85 A-1220 S(═O)₂CF₃ H H-86 A-1221 S(═O)₂CF₃ H H-87 A-1222 S(═O)₂CF₃ H H-88 A-1223 S(═O)₂CF₃ H H-89 A-1224 S(═O)₂CF₃ H H-90 A-1225 S(═O)₂CF₃ H H-91 A-1226 S(═O)₂CF₃ H H-92 A-1227 S(═O)₂CF₃ H H-93 A-1228 S(═O)₂CF₃ H H-94 A-1229 S(═O)₂CF₃ H H-95 A-1230 S(═O)₂CF₃ H H-96 A-1231 S(═O)₂CF₃ H H-97 A-1232 S(═O)₂CF₃ H H-98 A-1233 S(═O)₂CF₃ H H-99 A-1234 S(═O)₂CF₃ H H-100 A-1235 S(═O)₂CF₃ H H-101 A-1236 S(═O)₂CF₃ H H-102 A-1237 S(═O)₂CF₃ H H-103 A-1238 S(═O)₂CF₃ H H-104 A-1239 S(═O)₂CF₃ H H-105 A-1240 S(═O)₂CF₃ H H-106 A-1241 S(═O)₂CF₃ H H-107 A-1242 S(═O)₂CF₃ H H-108 A-1243 S(═O)₂CF₃ H H-109 A-1244 S(═O)₂CF₃ H H-110 A-1245 S(═O)₂CF₃ H H-111 A-1246 S(═O)₂CF₃ H H-112 A-1247 S(═O)₂CF₃ H H-113 A-1248 S(═O)₂CF₃ H H-114 A-1249 S(═O)₂CF₃ H H-115 A-1250 S(═O)₂CF₃ H H-116 A-1251 S(═O)₂CF₃ H H-117 A-1252 S(═O)₂CF₃ H H-118 A-1253 S(═O)₂CF₃ H H-119 A-1254 S(═O)₂CF₃ H H-120 A-1255 S(═O)₂CF₃ H H-121 A-1256 S(═O)₂CF₃ H H-122 A-1257 S(═O)₂CF₃ H H-123 A-1258 S(═O)₂CF₃ H H-124 A-1259 S(═O)₂CF₃ H H-125 A-1260 S(═O)₂CF₃ H H-126 A-1261 S(═O)₂CF₃ H H-127 A-1262 S(═O)₂CF₃ H H-128 A-1263 S(═O)₂CF₃ H H-129 A-1264 S(═O)₂CF₃ H H-130 A-1265 S(═O)₂CF₃ H H-131 A-1266 S(═O)₂CF₃ H H-132 A-1267 S(═O)₂CF₃ H H-133 A-1268 S(═O)₂CF₃ H H-134 A-1269 S(═O)₂CF₃ H H-135 A-1270 S(═O)₂CF₃ H H-136 A-1271 S(═O)₂CF₃ H H-137 A-1272 S(═O)₂CF₃ H H-138 A-1273 S(═O)₂CF₃ H H-139 A-1274 S(═O)₂CF₃ H H-140 A-1275 S(═O)₂CF₃ H H-141 A-1276 S(═O)₂CF₃ H H-142 A-1277 S(═O)₂CF₃ H H-143 A-1278 S(═O)₂CF₃ H H-144 A-1279 S(═O)₂CF₃ H H-145 A-1280 S(═O)₂CF₃ H H-146 A-1281 S(═O)₂CF₃ H H-147 A-1282 S(═O)₂CF₃ H H-148 A-1283 S(═O)₂CF₃ H H-149 A-1284 S(═O)₂CF₃ H H-150 A-1285 S(═O)₂CF₃ H H-151 A-1286 S(═O)₂CF₃ H H-152 A-1287 S(═O)₂CF₃ H H-153 A-1288 S(═O)₂CF₃ H H-154 A-1289 S(═O)₂CF₃ H H-155 A-1290 S(═O)₂CF₃ H H-156 A-1291 S(═O)₂CF₃ H H-157 A-1292 S(═O)₂CF₃ H H-158 A-1293 S(═O)₂CF₃ H H-159 A-1294 S(═O)₂CF₃ H H-160 A-1295 S(═O)₂CF₃ H H-161 A-1296 S(═O)₂CF₃ H H-162 Combination of meanings for R¹, R², and moiety of formula (H)

Also preferred are the compounds of formula (I) corresponding to the compounds as disclosed in Table 1 to Table 90, wherein R^(w) is CH₃ instead of C₂H₅.

Also preffered are the compounds of formula (I) corresponding to the compounds as disclosed in Table 1 to Table 90, wherein R^(w) is C₃H₇ instead of C₂H₅.

In a preferred embodiment, the compound os formula (I) is a compound of formula (I.A) or (I.B), wherein the moiety of formula (H) is selected from H-1 to H-9, H-17 to H-25, H-33 to H-41, H-49 to H-57, H-66 to H-73, H-81 to H-89, H-97 to H-105, H-113 to H-121, and H-129 to H-137, and wherein

-   R¹ is H, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-sulfenyl, C₁-C₆-sulfinyl,     or C₁-C₆-sulfonyl, which groups are unsubstituted or halogenated; -   R² is H, or C₁-C₃-alkyl; -   R³ is C₁-C₃-alkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl,     C₁-C₃-alkoxy-C₁-C₃-alkyl, C₃-C₃-cycloalkyl, phenyl, benzyl,     C₃-C₆-cycloalkyl-C₁C₃-alkyl, which groups are unsubstituted or     halogenated; -   R⁴ is C₁-C₃-alkyl or H; -   R⁵ is C₁-C₃-alkyl; -   R⁶ is H, or C₁-C₃-alkyl; -   X is O or S.

In a another preferred embodiment, the compound os formula (I) is a compound of formula (I.A) wherein the moiety of formula (H) is selected from H-1 to H-162, preferably H-33 to H-48, H-81 to H-96, H-160, H-151, H-152, H-161, and H-163, and wherein

-   R¹ is C₁-C₃-alkyl, which groups are unsubstituted or halogenated,     preferably CF₃; -   R² H, halogen; C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl,     C₂-C₃-alkynyl, which groups are unsubstituted or halogenated,     preferably H, -   R³ C₁-C₃-alkyl, cyclopropyl, cyclopropyl-C₁-C₂-alkyl, which groups     are unsubstituted or halogenated, preferably unsubstituted; -   R⁶ is H, or CH₃, preferably H; -   X is O.

The invention also relates to a mixture of at least one compound of formula (I) with at least one mixing partner. Preferred are binary mixtures of one compound of formula (I) as component I with one mixing partner herein as component II. Preferred weight ratios for such binary mixtures are from 5000:1 to 1:5000, preferably from 1000:1 to 1:1000, more preferably from 100:1 to 1:100, particularly from 10:1 to 1:10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.

Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers. Preferred mixing partners are insecticides, nematicides, and fungicides.

The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of formula (I). An agrochemical composition comprises a pesticidally effective amount of a compound of formula (I).

The compounds of formula (I) can be converted into customary types of agro-chemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials e.g. seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. The compositions are prepared in a known manner, e.g. described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable solvents and liquid carriers are water and organic solvents. Suitable solid carriers or fillers are mineral earths. Suitable surfactants are surface-active compounds, e.g. anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & Detergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants. Suitable cationic surfactants are qua-ternary surfactants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100%. Various types of oils, wetters, adjuvants, or fertilizer may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1. The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agro-chemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

The compounds of formula (I) are suitable for use in protecting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of formula (I).

The compounds of formula (I) are also suitable for use in combating or controlling animal pests. Therefore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, e.g. seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of formula (I).

The compounds of formula (I) are effective through both contact and ingestion to any and all developmental stages, such as egg, larva, pupa, and adult. The compounds of formula (I) can be applied as such or in form of compositions comprising them.

The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials by the pests. The term “contacting” includes both direct contact (applying the compounds/compositions directly on the animal pest or plant) and indirect contact (applying the compounds/compositions to the locus).

The term “animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.

The term “plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet, or fodder beet; fruits, e.g. pomes, stone fruits, or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, e.g. beans, lentils, peas, alfalfa, or soybeans; oil plants, e.g. rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e.g. squashes, pumpkins, cucumber or melons; fiber plants, e.g. cotton, flax, hemp, or jute; citrus fruit, e.g. oranges, lemons, grape-fruits or mandarins; vegetables, e.g. eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, e.g. avocados, cinnamon, or camphor; energy and raw material plants, e.g. corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines; hop; sweet leaf (Stevia); natural rubber plants or ornamental and forestry plants, , shrubs, broad-leaved trees or evergreens, eucalyptus; turf; lawn; grass. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee, or sugar cane; fruits; vines; ornamentals; or vegetables, e.g. cucumbers, tomatoes, beans or squashes.

The term “seed” embraces seeds and plant propagules including true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots, and means preferably true seeds.

“Pesticidally effective amount” means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions e.g. desired pesticidal effect and duration, weather, target species, locus, mode of application.

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.

The compounds of formula (I) are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds of formula (I) can be used as bait composition, gel, general insect spray, aero-sol, as ultra-low volume application and bed net (impregnated or surface applied).

The term “non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, e.g. ants, termites, wasps, flies, ticks, mosquitoes, bed bugs, crickets, or cockroaches, such as: Aedes aegypti, Musca domestica, Tribolium spp.; termites such as Reticulitermesflavipes, Coptotermes formosanus; roaches such as Blatella germanica, Periplaneta Americana; ants such as Solenopsis invicta, Linepithema humile, and Camponotus pennsylvanicus.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). For use in bait compositions, the typical content of active ingredient is from 0.001 wt% to 15 wt%, desirably from 0.001 wt% to 5 wt% of active compound.

The compounds of formula (I) and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants, termites and/or wood or textile destroying beetles, and for controlling ants and termites from doing harm to crops or human beings (e.g. when the pests invade into houses and public facilities or nest in yards, orchards or parks).

Customary application rates in the protection of materials are, e.g., from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 wt%, preferably from 0.1 to 45 wt%, and more preferably from 1 to 25 wt% of at least one repellent and/or insecticide.

Pests

The compounds of the invention are especially suitable for efficiently combating animal pests e.g. arthropods, and nematodes including:

-   insects from the sub-order of Auchenorrhyncha, e.g. Amrasca     biguttula, Empoasca spp., Nephotettix virescens, Sogatella     furcifera, Mahanarva spp., Laodelphax striatellus, Nilaparvata     lugens, Diaphorina citri; -   Lepidoptera, e.g. Helicoverpa spp., Heliothis virescens, Lobesia     botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia     includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni,     Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo     suppressalis, Anticarsia gemmatalis, Agrotis ipsilon, Chrysodeixis     includens; -   True bugs, e.g. Lygus spp., Stink bugs such as Euschistus spp.,     Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops     furcatus; -   Thrips, e.g. Frankliniella spp., Thrips spp., Dichromothrips     corbettii; -   Aphids, e.g. Acyrthosiphon pisum, Aphis spp., Myzus persicae,     Rhopalosiphum spp., Schizaphis graminum, Megoura viciae; -   Whiteflies, e.g. Trialeurodes vaporariorum, Bemisia spp.; -   Coleoptera, e.g. Phyllotreta spp., Melanotus spp., Meligethes     aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica     spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Popilla     spp., Epilachna spp.; -   Flies, e.g. Delia spp., Ceratitis capitate, Bactrocera spp.,     Liriomyza spp.; -   Coccoidea, e.g. Aonidiella aurantia, Ferrisia virgate; -   Anthropods of class Arachnida (Mites), e.g. Penthaleus major,     Tetranychus spp.; Nematodes, e.g. Heterodera glycines, Meloidogyne     spp., Pratylenchus spp., Caenorhabditis elegans.

The compounds of formula (I) are also especially suitable for controlling pests from the family of Pentatomidae, such as Acrosternum spp., Euschistus spp., Halyomorpha spp., Nezara spp., Megacopta spp., and Piezodorus spp., in particular Euschistus servus (brown stink bug), Euschistus heros (Neotropical brown stink bug), Halyomorpha halys (brown marmorated stink bug), Nezara viridula (southern green stink bug), Megacopta cribraria (globular stink bug), and Piezodorus guildini and soil pests like Popilla japonica.

Animal Health

The compounds of formula (I) are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the invention also relates to the use of a compound of the invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the invention relates to a method of treating or protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I).

The invention also relates to the non-therapeutic use of compounds of the invention for treating or protecting animals against infestation and infection by parasites. Moreover, the invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of formula (I).

The compounds of the invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of formula (I).

The invention also relates to the non-therapeutic use of compounds of formula (I) for controlling or combating parasites. Moreover, the invention relates to a non-therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of formula (I).

The compounds of formula (I) can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of formula (I) can be applied to any and all developmental stages.

The compounds of formula (I) can be applied as such or in form of compositions comprising them.

The term “locus” means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.

As used herein, the term “parasites” includes endo- and ectoparasites. In some embodiments of the invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. Infestations in warm-blooded animals and fish include lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.

The compounds of the invention are especially useful for combating the following parasites: Cimex lectularius, Rhipicephalus sanguineus, and Ctenocephalides felis.

As used herein, the term “animal” includes warm-blooded animals (including humans) and fish. Preferred are mammals, such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in furbearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Particularly preferred are domestic animals, such as dogs or cats.

The compounds of formula (I) may be applied in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

For oral administration to warm-blooded animals, the compounds of formula (I) may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula (I), preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the compounds of formula (I) may be administered to animals parenterally, e.g., by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula (I) may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula (I) may be formulated into an implant for subcutaneous administration. In addition the compounds of formula (I) may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula (I).

The compounds of formula (I) may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of formula (I). In addition, the compounds of formula (I) may be formulated as ear tags for animals, particularly quadrupeds e.g. cattle and sheep.

Oral solutions are administered directly.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.

Gels are applied to or spread on the skin or introduced into body cavities.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound of formula (I)n suitable skin-compatible solvents or solvent mixtures.

Emulsions can be administered orally, dermally or as injections.

Suspensions can be administered orally or topically/dermally.

Semi-solid preparations can be administered orally or topically/dermally.

For the production of solid preparations, the active compound of formula (I)s mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form. The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula (I).

Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80% by weight, preferably from 0.1 to 65% by weight, more preferably from 1 to 50% by weight, most preferably from 5 to 40% by weight. Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90% by weight, preferably of 1 to 50% by weight.

Furthermore, the preparations comprise the compounds of formula I against endoparasites in concentrations of 10 ppm to 2% by weight, preferably of 0.05 to 0.9% by weight, very particularly preferably of 0.005 to 0.25% by weight.

Solid formulations which release compounds of the invention may be applied in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.

The following examples illustrate the invention.

A. Preparation of Compounds

Materials: Unless otherwise noted, reagents and solvents were purchased at highest commercial quality and used without further purification.

All reactions were monitored by thin-layer chromatography (TLC) using Merck silica gel 60 F₂54 pre-coated plates (0.25 mm). Flash chromatography was carried out with Kanto Chemical silica gel (Kanto Chemical, silica gel 60N, spherical neutral, 0.040-0.050 mm, Cat.-No. 37563-84). ¹H NMR spectra were recorded on JEOL JNM-ECA-500 (500 MHz). Chemical shifts are expressed in ppm downfield from the internal solvent peaks for acetone-d₆ (¹H; δ = 2.05 ppm) and CD₃OD (¹H; δ = 3.30 ppm), and J values are given in Hertz. The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, dd = double doublet, dt = double triplet, m = multiplet, br = broad. High-resolution mass spectra were measured on a JEOL JMS-T100LP.

Characterization: The compounds were characterized by coupled High Performance Liquid Chromatography with mass spectrometry (HPLC/MS).

UHPLC-MS on Shimadzu LCMS 2020 ESI. Analytical UHPLC column: C-18 , 50 mm , 4.6 mm , 5 micron; mobile phase: 100 mM Ammonium Formate B : Acetonitrile Flow Rate : 1.2 mL/min, Injection Vol : 1 µL in 1.50 minutes; Gradient: 10% B to 100% B in 1.5 min, Hold 100% B for 1 min , 2.51 min 10% B Run time : 3 min at 400° C. MS-method: ESI positive; mass range (m/z) 100-800.

General abbreviations used: DMF is dimethylformamide; min is minutes; THF is tetrahydrofuran; DCM is dichlormethane; mL is milliliters

Synthesis Example 1: Manufacture of 2-[5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (compound C-5)

Step 1) Preparation of 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-N-methoxy-N-methylpyridine-2-carboxamide: To a solution of 2.4 mmol 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (WO 2018/153778, p.57) and 4.79 mmol N,O-dimethyl hydroxylamine in 15 ml DMF were added 1.6 ml diisopropylethylamine and 1.37 g HATU and the mixture was stirred for 12 hours at 20 to 25° C. The reaction was concentrated under reduced pressure to afford a crude residue. The crude residue was taken up in ethyl acetate and washed two times with H₂O. The combined organic layers were dried and concentrated under reduced pressure to afford a residue. The residue was purified by column chromatography under reversed phase conditions to afford 400 mg 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-N-methoxy-N-methyl-pyridine-2-carboxamide. LC-MS: mass found for C₁₄H₁₉N₃O₂S [M+H]⁺ 293.8; t_(R)= 0.919 min (t_(R): retention time).

Step 2) Preparation of 2-(6-acetyl-5-ethylsulfanyl-3-pyridyl)-2-methyl-propanenitrile To a solution of 1.36 mmol 5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-N-methoxy-N-methylpyridine-2-carboxamide in 5 ml THF were added 0.91 ml of a 3 molar solution of CH₃MgBr in diethyl ether at 0° C. under N₂-atmosphere. The resulting composition was warmed to 20 to 25° C. and stirred for additional 60 minutes. The composition was then diluted with ethyl acetate and a saturated aqueous solution of NH₄Cl. The aqueous layer was separated and extracted twice with ethyl acetate. The combined organic layers were dried and concentrated under reduced pressure to afford 318 mg 2-(6-acetyl-5-ethylsulfanyl-3-pyridyl)-2-methyl-propanenitrile. The crude product was used in the next step without further purification.

Step 3) Preparation of 2-[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]-2-methyl-propanenitrile: A solution of 1.28 mmol 2-(6-acetyl-5-ethylsulfanyl-3-pyridyl)-2-methyl-propanenitrile was dissolved in 1.5 ml 25% HBr in CH₃COOHacetic acid and a solution of 1.41 mmol Br₂ in 1.5 ml CH₃COOH was added at 20 to 25° C. and stirred for 12 hours. The reaction was concentrated under reduced pressure to afford a crude residue. The crude residue was taken up in ethyl acetate and washed two times with H₂O. The combined organic layers were dried and concentrated under reduced pressure to afford the crude product. The crude product was used in the next step without further purification.

Step 4) Preparation of 2-[5-ethylsulfanyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile: A solution of 1.28 mmol 2-[6-(2-bromoacetyl)-5-ethylsulfanyl-3-pyridyl]-2-methyl-propanenitrile and 1.07 mmol 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one was dissolved in 8 ml (CH₃)₃COH and heated to refluxation for 3 days. The reaction was then cooled to 20 to 25° C. and concentrated under reduced pressure to afford a crude residue. The crude residue was taken up in ethyl acetate and washed two times with H₂O. The organic layer was dried and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by preparative HPLC to afford 46 mg of 2-[5-ethylsulfanyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)-imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile.

LC-MS: mass found for C₁₉H₁₈F₃N₅OS [M+H]⁺ 421.8; t_(R)= 1.101 min.

Step 5) Preparation of 2-[5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile: To a solution of 2-[5-ethylsulfanyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile (0.11 mmol) in CH₃COOH (2 mL) was added sodium tungstate (0.003 mmol) and H₂O₂ (30% solution in H₂O, 0.22 mmol). The resulting reaction mixture was stirred at 20 to 25° C. for approximately 12 hours and then concentrated under reduced pressure to obtain a crude residue. The crude residue was taken up in ethyl acetate and washed two times with an aqueous saturated solution of NaHCO₃. The organic layer was dried and concentrated under reduced pressure to afford a residue. 2-[5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-3-pyridyl]-2-methyl-propanenitrile was obtained in sufficient purity (43 mg). mass found for C₁₉H₁₈F₃N₅O₃S [M+H]⁺ 454.0 ; t_(R)= 1.063 min.

Synthesis Example 2: Preparation of 1-r6-r6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile (compound C-6) Step 1): Manufacture of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile

A composition containing 5-bromo-3-nitro-pyridine-2-carbonitrile (0.087 mol) in DMF (200 mL) was prepared under stirring at -40° C., upon which sodium ethane thiolate was added (0.105 mol) portion wise over a period of 30 min under N₂-atmosphere at maintained temp between -40 to -50° C. The resulting reaction mixture was stirred at the same temperature for 10 minutes, then gradually allowed to reach 20 to 25° C. with continued stirring for 1 hour. After the completion of reaction, the reaction mixture was quenched and extracted with CH₃COOCH₂CH₃. The organic layers were washed, dried and concentrated under reduced pressure to get a crude residue. The crude residue was purified by column chromatography to afford 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile as a yellow solid (17 g). H¹-NMR (500 MHz, CDCl₃): δ 8.52 (s, 1H), 7.85 (s, 1H), 3.07 (q, 2H, J= 10 Hz), 1.43 (t, 3H, J = 7.3 Hz). LC-MS: mass found for C₈H₇BrN₂S [M+H]⁺ found 244.

Step 2): Manufacture of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone

A composition containing 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (17 g) in THF (170 mL) was prepared under stirring at 0° C., upon which CH₃MgBr (2 eq) was added dropwise over a period of 30 min at 0° C. to -5° C. under N₂-atmosphere. The resulting reaction mixture was stired at 0° C. for 2 hours. After the completion of reaction, the reaction mixture was quenched and extracted. The organic layers were washed, dried and concentrated under reduced pressure to get crude residue. The crude residue was purified by crystallization. After treatment with CH₃COOCH₂CH₃ and heptane at -30° C., a precipitate was observed. The obtained solid was filtered and dried under reduced pressure to afford 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (14 g). H¹ NMR (500 MHz, DMSO): δ 8.57 (s, 1H), 8.05 (s, 1H), 3.01 (q, 2H, J = 10 Hz), 2.59 (s, 3H), 1.26 (t, 3H, J = 7.3 Hz). LC-MS: mass found for C₉H₁₀BrNOS [M+H]⁺ 261.

Step: Manufacture of 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone

A composition containing 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (3.9 g) in CH₂CI₂ (40 mL) was prepared under stirring at 0° C., upon which m-chloroperoxy benzoic acid was added (0.039 mol). The resulting reaction mixture was stirred at 20 to 25° C. for 3 to 4 hours. After the completion of reaction, the reaction mixture was quenched, and extracted with CH₂Cl₂. The combined organic layers were washed, dried and concentrated under reduced pressure to afford 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone (3.2 g). H¹ NMR (500 MHz, CDCl₃): δ9.12 (s, 1H), 8.55 (s, 1H), 3.55 (q, 2H J= 12 Hz), 2.5 (s, 3H),1.20 (t, 3H, J= 7 Hz). LC-MS: mass found for C₉H₁₀BrNO₃S [M+H]⁺ 292.

Step-4: Manufacture of 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone

A composition containing 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone (0.010 mol) in CHCl₃ (30 mL) was prepared under stirring at 0° C., upon which CH₃COOH (30 mL) and HBr in CH₃COOH (30 mL) were added and stirred for few minutes. Then, Br₂ (0.012 mol) in CHCl₃ was added. The resulting reaction mixture was heated to 60° C. for 1 hour. After the completion of reaction, the reaction mixture was quenched, and extracted with CH₂CI₂. The combined organic layers were washed, dried, and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by column chromatography to afford 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone (2.2 g). H¹ NMR (500 MHz, CDCl₃): δ 9.17 (s, 1H), 8.63 (s, 1H), 4.92 (s, 2H), 3.59 (q, 2H J= 12 Hz), 1.20 (t, 3H, J= 7 Hz). LC-MS: mass found for C₉H₉Br₂NO₃S [M+H]⁺ 372.

Step 5): Manufacture of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A composition containing 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone (0.006 mol) in (CH₃)₃COH (4 mL) was prepared under stirring, upon which 1-cyclopropyl-4-imino-6-(trifluoromethyl)pyrimidin-2-one (0.036 mol) was added. Molecular sieves were added to the above reaction mixture (2 g) and the resultant reaction mixture was heated to 120° C. for 24 hours. After the completion of reaction, the reaction mixture was filtered through celite bed, and the filtrate was collected and concentrated under reduced pressure to get a crude residue. The crude residue was purified by column chromatography to afford 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (1.5 g). H¹-NMR (500 MHz, DMSO): δ 9.10 (s, 1H), 8.53 (s, 1H), 8.28 (s, 1H), 7.52 (s, 1H), 4.06 (q, 2H, J = 10 Hz), 3.17 (s, 1H), 1.23 (t, 3H, J= 7 Hz), 1.09 ( dd, 4H, J= 4.5 Hz). LC-MS: mass found for C₁₇H₁₄BrF₃N₄O₃S [M+H]⁺ found 492.

Step 6): Manufacture of 2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]acetonitrile

A composition containing 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (2.0396 mmol) in DMF (5 mL) was prepared at 25° C., upon which 2-trimethylsilylacetonitrile (2.4475 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.0510 mmol), and xantphos (0.1020 mmol) were added. The resulting reaction mixture was degassed for 15 minutes under N₂-atmosphere, followed by the addition of ZnF₂ (1.2238 mmol). The reaction mixture was then heated to 120° C. for 12 hours in a Radley’s reactor. After the completion of the reaction, the reaction mixture was quenched with H₂O, and extracted with CH₃COOCH₂CH₃. The combined organic layers were washed, dried, and concentrated under reduced pressure to get a crude residue. The crude residue was purified by column chromatography to afford 2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]acetonitrile (0.220 g). H¹-NMR (500 MHz, DMSO-d6): δ 9.10 (d, J = 2.4 Hz, 1H), 8.45 (d, J = 2.4 Hz, 1H), 8.28 (s, 1H), 7.51 (s, 1H), 4.07 (q, J = 7.3 Hz, 2H), 3.86 (s, 2H), 3.17 (s, 1H), 1.25 (t, J = 7.4 Hz, 3H), 1.19 -1.00 (m, 4H). LC-MS: mass found for C₁₉H₁₆F₃N₅O₃S [M+H]⁺ 452.0.

Step 7): Manufacture of 1-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile

A composition comprising 2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]acetonitrile (0.31 mmol) and K₂CO₃ (0.624 mmol) in CH₃CN (2 mL) was prepared under stirring at 0° C., upon which 1-chloro-2-bromoethane (0.66 mmol) was added dropwise. The resulting reaction mixture was stirred at 20 to 25° C. for 1 to 2 hours. After the completion of the reaction, the reaction mixture was quenched with H₂O and extracted with CH₃COOCH₂CH₃. The combined organic layers were dried and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by column chromatography to afford 1-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile (0.1 g). H¹-NMR (500 MHz, DMSO-d6): ¹H NMR (500 MHz, DMSO-d₆): δ 8.84 (d, J= 2.4 Hz, 1H), 8.35 (d, J= 2.4 Hz, 1H), 8.25 (s, 1H), 7.51 (s, 1H), 4.07 (q, J = 7.3 Hz, 2H), 3.17 (s, 1H), 2.03 - 1.87 (m, 2H), 1.87 - 1.73 (m, 2H), 1.25 (t, J = 7.4 Hz, 3H), 1.19 - 1.00 (m, 4H). LC-MS: mass found for C₂₁H₁₈F₃N₅O₃S [M+H]⁺ 478.0.

Synthesis Example 3: 2-[3-ethylsulfonyl-5-[(E)-2,2,2-trifluoroethoxviminomethyl]-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound C-3) Step 1): Preparation of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A composition of 16 mmol of 2-bromo-1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone (WO2016/071214, p.78) and 4-amino-1-methyl-6-(trifluoromethyl)pyrimidin-2-one (16 mmol) was in 10 ml (CH₃)₃COH was prepared and heated to refluxation for 12 hours. The resulting reaction mixture was then cooled to 20 to 25° C. and the precipitate was collected by filtration to afford 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo-[1,2-c]pyrimidin-5-one (5 g).

LC-MS: mass found for C₁₅H₁₂N₄O₃F₃SBr [M+H]⁺ 466.9; t_(R)= 1.122 min.

Step 2): Preparation of 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A composition comprising 5 mmol of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo-[1,2-c]pyrimidin-5-one, 7.7 mmol of tributyl(vinyl)tin and 0.42 g 1,1′-bis(diphenylphospino)ferrocene Pd(II) dichloride in 200 ml toluene was prepared and stirred at 100° C. for 36 hours. The composition was then cooled to 20 to 25° C. and washed with an aqueous saturated solution of KF. The combined organic layers were dried, and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by column chromatography to afford 1.4 g of 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one. LC-MS: mass found for C₁₇H₁₅N₄O₃F₃S [M+H]⁺ 413.0; t_(R)= 1.067 min.

Step 3): Preparation of 5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]pyridine-3-carbaldehyde

To a composition containing 3.4 mmol of 2-(3-ethylsulfonyl-5-vinyl-2-pyridyl)-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one in 50 ml THF/water (1:1) was added a solution of OsO₄ in (CH₃)₃COH (2.5%, 1 g) and 6.8 mmol NalO₄ at 0° C. The resulting reaction mixture was slowly warmed to 20 to 25° C. and stirred for approximately 12 hours. The reaction mixture was quenched with a saturated aqueous solution of sodium thiosulfate, and extracted with CH₃COOHCH₂CH₃. The combined organic layers were dried and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by column chromatography under reversed phase conditions to afford 1 g of 5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]pyridine-3-carbaldehyde. LC-MS: mass found for C₁₆H₁₃N₄O₄F₃S [M+H]⁺ 432.9.0 (hydrate); t_(R)= 0.976 min.

Step 4): Preparation of 2-[3-ethylsulfonyl-5-[(E)-2,2,2-trifluoroethoxyiminomethyl]-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A composition comprising 0.14 mmol of 5-ethylsulfonyl-6-[6-methyl-5-oxo-7-(trifluoromethyl)-imidazo[1,2-c]pyrimidin-2-yl]pyridine-3-carbaldehyde and 2 ml CH₃CH₂OH was added 0.16 mmol 2,2,2-trifluoroethoxyammonium chloride and 15 mg (CH₃CH₂)₃N. The resulting reaction mixture was stirred at 60° C. for 4 hours and then concentrated under reduced pressure to obtain a crude residue. The residue was taken up in H₂O and extracted with CH₂Cl₂. The combined organic layers were dried and concentrated under reduced pressure to afford a crude residue. The crude residue was purified by column chromatography under reversed phase conditions to afford 18 mg of 2-[3-ethylsulfonyl-5-[(E)-2,2,2-trifluoroethoxyiminomethyl]-2-pyridyl]-6-methyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one. LC-MS: mass found for C₁₈H₁₅N₅O₄F₆S [M+H]⁺ 511.8; t_(R)= 1.192 min.

Synthesis Example 4: Manufacture of (2Z)-2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]-2-hydroxyimino-acetonitrile (compound C-8)

To a stirred composition of 2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]acetonitrile (1.77 mmol) and sodium methoxide (5.3 mmol) in CH₃CH₂OH (8 mL) at 0° C. was added isopentyl-nitrite (3.5 mmol) dropwise. The resulting reaction mixture was stirred at 20 to 25° C. for 16 hours. After the completion of the reaction, the reaction mixture was quenched with H₂O and extracted with CH₃COOCH₂CH₃. The combined organic layers were separated, dried and concentrated to afford a crude residue. The crude residue was purified by column chromatography to afford (2Z)-2-[6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-3-pyridyl]-2-hydroxyimino-acetonitrile as a pale yellow solid (0.7 g, 81% yield). ¹H-NMR (500 MHz, DMSO-d6): δ 9.22 (s, 1H), 8.48 (s, 1H), 8.20 (d, J = 3.1 Hz, 1H), 7.49 (s, 1H), 5.76 (s, 2H), 3.17 (s, 1H), 1.22 (dt, J = 10.8, 7.4 Hz, 3H), 1.18 - 0.94 (m, 4H). LC-MS: mass found for C₁₉H₁₅F₃N₆O₄S [M+H]⁺ 481.0.

Synthesis Example 5: Manufacture of 6-cyclopropyl-2-[3-ethylsulfonyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (compound C-13) Step 1): Synthesis of 6-cyclopropyl-2-[3-(ethanesulfonyl)-5-ethenylpyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A composition comprising 2-[5-bromo-3-(ethane sulfonyl) pyridin-2-yl]-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (2.036 mmol) in dry 1,4 dioxane (20 ml) was added tributyl(vinyl)tin (2.504 mmol) and the resulting reaction mixture was purged with a nitrogen balloon for 5 minutes. Then, 1,1′-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.3054 mmol) was added and the reaction mixture was heated for 18 hours to 100° C. The reaction mixture was poured in H₂O (30 ml) and CH₃COOCH₂CH₃ (60 ml) was added. The resulting mixture was filtered through a celite bed; the filtrate was collected and extracted. The combined organic extracts were dried and concentrated under reduced pressure to afford a crude product. The crude product was purified by column chromatography to afford 6-cyclopropyl-2-[3-(ethanesulfonyl)-5-ethenylpyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a beige solid (0.75 g). H¹-NMR (500 MHz, DMSO-d6): δ 9.07 (d, J = 2.1 Hz, 1H), 8.44 (d, J = 2.1 Hz, 1H), 8.26 (s, 1H), 7.51 (s, 1H), 6.97 (dd, J = 17.8, 11.1 Hz, 1H), 6.20 (d, J = 17.8 Hz, 1H), 5.60 (d, J = 11.1 Hz, 1H), 4.05 (q, J = 7.4 Hz, 2H), 3.18 (d, J = 4.5 Hz, 1H), 1.24 (t, 3H), 1.15 (m, 2H), 1.11 (m, 2H). LC-MS: mass found for C₁₉H₁₇F₃N₄O₃S [M+H]⁺ 439.0.

Step 2): Synthesis of 6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-(ethanesulfonyl)pyridine-3-carbaldehyde

To a composition of 6-cyclopropyl-2-[3-(ethanesulfonyl)-5-ethenylpyridin-2-yl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (4.675 mmol) in dry 1,4 dioxane (30 ml) was added OsO₄ (1.660 mmol) at 0° C. and the resulting reaction mixture was stirred for 5 min upon which NalO₄ was added (23.401 mmol). The reaction mixture was then stirred for 18 hours at 25° C. Subsequently, the reaction mixture was poured into H₂O water (60 ml) and extracted. The combined organic layers were dried and concentrated under reduced pressure to afford the crude product. The crude product was purified by column chromatography to afford 6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-(ethanesulfonyl)pyridine-3-carbaldehyde (1.5 g). H¹ NMR (500 MHz, DMSO-d6): δ 9.11 (d, J = 2.1 Hz, 1H), 8.55 (d, J = 2.1 Hz, 1H), 8.31 (s, 1H), 7.43 (s, 1H), 3.83 (d, J = 7.4 Hz, 2H), 3.10 (d, J = 4.4 Hz, 1H), 1.17 (t, J = 7.4 Hz, 3H), 1.14 - 1.02 (m, 5H). LC-MS: mass found for C₁₈H₁₅F₃N₄O₄S [M+H]⁺ 441.0.

Step 3): Synthesis of (3E)-6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-pyridine-3-carbaldehyde oxime (compound I.x)

To a composition comprising 6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-pyridine-3-carbaldehyde (0.15 g, 0.340 mmol) in dry CH₃OH (5 ml) was added [NH₃OH]Cl (0.3747 mmol) at 25° C. and the resulting reaction mixture was stirred for 18 hours at 25° C. After the completion the reaction, the reaction mixture was concentrated under reduced pressure to afford the crude product. The crude product was washed with (CH₃COOCH₂CH₃ : n-pentane in a ratio of 1:4), filtered and dried to afford (3E)-6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-pyridine-3-carbaldehyde oxime (0.122 g). H¹ NMR (500 MHz, DMSO-d6): 12.06 (s, 1H), 9.01 (d, J = 2.3 Hz, 1H), 8.59 (d, J = 2.1 Hz, 1H), 8.34 (s, 1H), 8.27 (s, 1H), 7.44 (s, 1H), 3.98 (d, J = 7.4 Hz, 2H), 3.27 - 3.09 (m, 1H), 1.19 (t, J = 7.5 Hz, 3H), 1.14 (m, J = 6.8 Hz, 2H), 1.05 (m, 2H). LC-MS: mass found for C₁₈H₁₆F₃N₅O₄S [M+H]⁺ 456.

Step 4): Manufacture of 6-cyclopropyl-2-[3-ethylsulfonyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)-2-pyridyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

To a stirred composition comprising (3E)-6-[6-cyclopropyl-5-oxo-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-2-yl]-5-ethylsulfonyl-pyridine-3-carbaldehyde oxime (0.21 mmol) in NaClO (10-15 wt% aqueous solution, 5 mL) and THF (5 V, 2 mL) at 0° C., was added methylene cyclopentane (0.018 mg, 0.21 mmol) dropwise. The resultant reaction mixture was stirred at 20 to 25° C. for 3 hours. After the completion of the reaction, the reaction mixture was quenched and extracted. The combined organic layers were, dried and concentrated under reduced pressure to afford a crude product. The crude product was purified by column chromatography to afford 6-cyclopropyl-2-[3-ethylsulfonyl-5-(1-oxa-2-azaspiro[4.4]non-2-en-3-yl)-2-pyridyl]-7-(trifluoromethyl)imidazo-[1,2-c]pyrimidin-5-one as an off white solid (0.55 g 45.84% yield). H¹ NMR (500 MHz, DMSO-d6): δ 9.10 (s, 1H), 8.59 (s,1H), 8.32 (s, 1H), 7.53 (s, 1H), 4.11 (d, J = 7.4 Hz, 2H), 3.52 (s, 2H), 3.17 (s, 1H), 1.97 (s, 3H), 1.86 - 1.60 (m, 8H), 1.34 - 1.18 (m, 2H), 1.10 (s, 2H). LC-MS: mass found for C₂₄H₂₄F₃N₅O₄S [M+H]⁺ 536.0.

Synthesis Example 6: Manufacture of 6-cyclopropyl-2-[2-ethylsulfonyl-4-[(E)-N-hydroxy-C-methyl-carbonimidoyl]phenyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (Compound C-21) Step 1): Manufacture of 2-(4-acetyl-2-ethylsulfonyl-phenyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

A stirred composition of 2-(4-bromo-2-ethylsulfonyl-phenyl)-6-cyclopropyl-7-(trifluoromethyl)-imidazo[1,2-c]pyrimidin-5-one (2.03 mmol) and tributyl(1-ethoxyvinyl)tin (2.03 mmol) in toluene (10 mL) was degassed under N₂-atmosphere for ten minutes, followed by addition of tetrakis-triphenylphosphin-palladium (1.04 mmol). The resultant reaction mixture was heated to 120° C. for 6 hours. After the completion of the reaction, the reaction mixture was quenched and extracted. The combined organic layer were dried and concentrated under reduced pressure to afford a crude product. The crude product was purified by column chromatography to afford 2-(4-acetyl-2-ethylsulfonyl-phenyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (0.88 g). H¹ NMR (500 MHz, DMSO-d6): δ 8.43 - 8.32 (m, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.96 (dd, J = 8.0, 1.8 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.59 (s, 1H), 4.33 (t, J = 7.4 Hz, 2H), 3.41 (d, J = 17.5 Hz, 3H), 3.17 (s, 1H), 2.70 (s, 3H),1.20 - 1.07 (m, 4H). LC-MS: mass found for C₂₀H₁₈F₃N₃O₄S [M+H]⁺ 454.0.

Step 2): Manufacture of 6-cyclopropyl-2-[2-ethylsulfonyl-4-[(E)-N-hydroxy-C-methyl-carbo-nimidoyl]phenyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one

To a stirred composition of 2-(4-acetyl-2-ethylsulfonyl-phenyl)-6-cyclopropyl-7-(trifluoromethyl)-imidazo[1,2-c]pyrimidin-5-one (0.79 mmol) in CH₃CH₂OH (5 mL) at 0° C. , was added [NH₃OH]Cl (0.95 mmol). The resultant reaction mixture was heated to 90° C. for 4 hours. After completion of the reaction, the reaction mixture was quenched and extracted. The combined organic layers were dried and concentrated under reduced pressure to afford a crude product. The crude product was purified by column chromatography to afford 6-cyclopropyl-2-[2-ethylsulfonyl-4-[(E)-N-hydroxy-C-methyl-carbonimidoyl]phenyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (0.23 g). H¹-NMR (500 MHz, DMSO-d6): δ 8.43 - 8.32 (m, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.96 (dd, J = 8.0, 1.8 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.59 (s, 1H), 4.33 (t, J = 7.4 Hz, 2H), 3.41 (d, J = 17.5 Hz, 3H), 3.17 (s, 1H), 2.70 (s, 3H),1.20 - 1.07 (m, 4H). LC-MS: mass found for C₂₀H₁₉F₃N₄O₄S [M+H]⁺ 469.0.

Synthesis Example 7: Manufacture of 6-cyclopropyl-2-[4-[(E)-N-(dimethylamino)-C-methyl-carbonimidoyl]-2-ethylsulfonyl-phenyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (Compound C-24)

To a stirred solution of 2-(4-acetyl-2-ethylsulfonyl-phenyl)-6-cyclopropyl-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one (0.44 mmol) in CH₃CH₂OH (2 mL) and CH₃COOH (0.05 mL) at 0° C., was added N,N-dimethylhydrazine (0.88 mmol). The resulting reaction mixture was heated to 80° C. for 1 hour. After the completion of the reaction, the reaction was quenched and the reaction mixture was extracted. Organic layer was separated, dried and concentrated to get a crude residue. The crude residue was purified by column chromatography to afford 6-cyclopropyl-2-[4-[(E)-N-(dimethylamino)-C-methyl-carbonimidoyl]-2-ethylsulfonyl-phenyl]-7-(trifluoromethyl)imidazo[1,2-c]pyrimidin-5-one as a pale yellow solid (0.05 g). ¹H-NMR (500 MHz, DMSO-d6): δ 8.47 (s, 1H), 8.29 (s, 1H), 8.11 (dd, J = 8.0, 1.8 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.49 (s, 1H), 3.61 (q, J= 7.3 Hz, 2H), 3.17 (s, 1H), 2.60 (s, 6H), 2.37 (s, 3H), 1.24 (s, 3H), 1.20 -1.07 (m, 4H). LC-MS: mass found for C₂₂H₂₄F₃N₅O₃S [M+H]⁺ 496.0.

With appropriate modification of the starting materials or intermediates thereof, the procedures as described in the preparation examples above were used to obtain further compounds as defined in Table B below.

TABLE B synthesized compounds of formula (I) and physical characterization data; n.m. means not measured Compound Structure Mass [M+H]⁺ in g/mol measured by HPLC-MS (retention time [min]) Chemical shift (δ) ¹H-NMR (in DMSO-d6 at 500 MHz or as provided below) C-1

443.8 (1.093) n.m. C-2

430 (0.968) n.m. C-3

511.9 (1.207) n.m. C-4

480 (1.845) δ 9.04 (s, 1H), 8.5 (s, 1H), 8.3 (s, 1H), 7.2 (s, 1H), 3.97 (q, 2H, J = 10 Hz), 3.2 (s, 1H), 1.85 (s, 6H), 1.30 (dd, 4H, J= 4.5 Hz), 1.26 (t, 3H, J= 7 Hz) C-5

454 (1.063) n.m. C-6

478 (1.786) 8.84 (d, J = 2.4 Hz, 1H), 8.35 (d, J = 2.4 Hz, 1H), 8.25 (s, 1H), 7.51 (s, 1H), 4.07 (q, J= 7.3 Hz, 2H), 3.17 (s, 1H), 2.03 - 1.87 (m, 2H), 1.87 - 1.73 (m, 2H), 1.25 (t, J= 7.4 Hz, 3H), 1.19 - 1.00 (m, 4H). C-7

494.0 (1.984) 9.16 (d, J = 2.3 Hz, 1H), 8.48 (d, J = 2.4 Hz, 1H), 8.36 (s, 1H), 7.61 (s, 1H), 4.06 (q, J= 7.4 Hz, 2H), 4.00 (d, J = 6.8 Hz, 2H), 1.87 - 1.80 (s, 6H), 1.7(m,1H), 1.29 - 1.21 (t, 3H), 0.85 (m, J = 6.6 Hz, 2H), 0.57 - 0.50 (m, 2H) C-8

481.0 (1.711) 9.22 (s, 1H), 8.48 (s, 1H), 8.20 (d, J = 3.1 Hz, 1H), 7.49 (s, 1H), 5.76 (s, 2H), 3.17 (s, 1H), 1.22 (dt, J = 10.8, 7.4 Hz, 3H), 1.18 -0.94 (m, 4H) C-9

495.0 (1.973) 9.16 (s, 1H), 8.62 (s, 1H), 8.30 (s, 1H), 7.54 (s, 1H), 4.29 (t, J = 20.6 Hz, 3H), 4.16 (q, J = 7.0 Hz, 2H), 3.17 (s, 1H), 1.25 (q, J = 7.8 Hz, 4H), 1.12 (t, J = 7.1 Hz, 3H) C-10

563.0 (2.056) 9.34 (s, 1H), 8.65 (s, 1H), 8.41 (s, 1H), 7.55 (s, 1H), 5.27 (dt, J = 23.2, 8.8 Hz, 2H), 4.16 (qd, J = 7.4, 1.9 Hz, 2H), 3.17 (s, 1H), 1.26 (q, J = 7.4 Hz, 3H), 1.20 -1.02 (m, 4H). C-11

535.0 (2.061) (CDCl₃): 9.17 (s, 1H), 8.61 (s, 1H), 8.37 (s, 1H), 7.54 (s, 1H), 4.34 (dd, J = 14.1, 7.4 Hz, 2H), 4.15 (q, J = 7.4 Hz, 2H), 3.18 (s, 2H), 1.26 (t, J = 7.4 Hz, 3H), 1.21 -1.02 (m, 4H), 0.63 (dt, J = 7.9, 3.1 Hz, 2H), 0.51 -0.35 (m, 2H). C-12

520.0 (1.816) 9.17 (s, 1H), 8.66 (s, 1H), 8.41 (s, 1H), 7.55 (s, 1H), 5.56 (s, 2H), 4.18 (q, J = 7.4 Hz, 2H), 3.18 (s, 1H), 1.27 (t, J= 7.4 Hz, 3H), 1.12 (dt, J= 25.1, 7.0 Hz, 4H). C-13

536.0 (1.985) 9.10 (s, 1H), 8.59 (s,1H), 8.32 (s, 1H), 7.53 (s, 1H), 4.11 (d, J= 7.4 Hz, 2H), 3.52 (s, 2H), 3.17 (s, 1H), 1.97 (s, 3H), 1.86 - 1.60 (m, 8H), 1.34 - 1.18 (m, 2H), 1.10 (s, 2H) C-14

484.0 (1.99) 9.09 (s, 1H), 8.63 (d, J = 2.0 Hz, 1H), 8.49 (d, J = 1.9 Hz, 1H), 8.31 (s, 1H), 7.52 (s, 1H), 4.26 (q, J = 7.0 Hz, 2H), 4.09 (q, J = 7.4 Hz, 2H), 3.20 - 3.14 (m, 1H), 1.30 (t, J = 7.1 Hz, 6H), 1.24 (m, J = 7.4 Hz, 2H), 1.19 (m,7.0 Hz, 2H) C-15

498.0 (2.05) 9.09 (s, 1H), 8.63 (d, J = 2.0 Hz, 1H), 8.46 (d, J = 1.9 Hz, 1H), 8.30 (s, 1H), 7.52 (s, 1H), 4.58 - 4.41 (m, 1H), 4.09 (q, J = 7.4 Hz, 2H), 3.23 - 3.12 (m, 1H), 1.33 (d, J = 6.2 Hz, 6H), 1.29 (m, J = 6.2 Hz, 3H), 1.24 (dd, J = 10.6, 6.8 Hz, 2H), 1.19 -1.04 (m, 2H) C-16

538.0 (1.89) 9.10 (d, J = 1.9 Hz, 1H), 8.72 (s, 1H), 8.67 (d, J = 2.0 Hz, 1H), 8.33 (s, 1H), 7.53 (s, 1H), 4.92 (q, J = 9.1 Hz, 2H), 4.11 (q, J = 7.4 Hz, 2H), 3.17 (s, 1H), 1.24 (t, J = 7.4 Hz, 3H), 1.15 (d, J = 7.0 Hz, 2H), 1.10 (s, 2H) C-17

479.0 (1.94) (300 MHz): 8.28 (s, 1H), 8.19 (d, J = 2.1 Hz, 1H), 7.99 (dd, J = 8.1, 2.2 Hz, 1H), 7.86 (d, J = 8.1 Hz, 1H), 7.50 (s, 1H), 3.66 (q, J = 7.3 Hz, 2H), 3.17 (s, 1H), 1.78 (s, 6H), 1.12 (m, 7H) C-18

477.0 (1.85) (300 MHz): 8.27 (s, 1H), 8.06 (d, J = 2.1 Hz, 1H), 7.81 (d, J = 8.1 Hz, 1H), 7.68 (dd, J = 8.1, 2.1 Hz, 1H), 7.49 (s, 1H), 3.65 (q, J = 7.3 Hz, 2H), 3.16 (s, 1H), 1.91 (t, J = 3.9 Hz, 2H), 1.75-1.61 (m, 2H), 1.12 (m, 7H) C-19

455.0 (1.717) 8.53 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 2.0 Hz, 1H), 7.96 (s, 1H), 7.43 (d, J = 0.8 Hz, 2H), 6.48 (s, 1H), 4.34 (s, 2H), 3.17 (s, 1H), 3.01 (q, J= 7.3 Hz, 3H), 1.20 (t, J= 7.3 Hz, 4H) C-20

536.0 (2.048) 8.68 (s, 1H), 8.44 - 8.26 (m, 2H), 8.04 (dd, J = 8.1, 1.8 Hz, 1H), 7.90 (s, 1H), 7.50 (s, 1H), 4.88 (q, J = 9.1 Hz, 2H), 3.66 (q, J = 7.4 Hz, 2H), 3.17 (s, 1H), 1.12 (m, 7H) C-21

469.0 (1.762) 8.43 - 8.32 (m, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.96 (dd, J = 8.0, 1.8 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.59 (s, 1H), 4.33 (t, J = 7.4 Hz, 2H), 3.41 (d, J = 17.5 Hz, 3H), 3.17 (s, 1H), 2.70 (s, 3H), 1.20 - 1.07 (m, 4H) C-22

551.0 (2.101) 8.37 (d, J= 1.9 Hz, 2H), 8.32 (s, 1H), 8.09 (s, 1H), 7.50 (s, 1H), 4.89 (q, J = 9.1 Hz, 2H), 3.65 (q, J= 7.3 Hz, 2H), 3.17 (s, 1H), 2.35 (s, 3H), 1.24 (t, J = 7.3 Hz, 3H), 1.02 (m, 4H) C-23

456.0 (1.671) 12.06 (s, 1H), 9.01 (d, J = 2.3 Hz, 1H), 8.59 (d, J = 2.1 Hz, 1H), 8.34 (s, 1H), 8.27 (s, 1H), 7.44 (s, 1H), 3.98 (d, J = 7.4 Hz, 2H), 3.27 -3.09 (m, 1H), 1.19 (t, J = 7.5 Hz, 3H), 1.14 (m, J = 6.8 Hz, 2H), 1.05 (m, 2H) C-24

496.0 (1.98) 8.47 (s, 1H), 8.29 (s, 1H), 8.11 (dd, J = 8.0, 1.8 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.49 (s, 1H), 3.61 (q, J = 7.3 Hz, 2H), 3.17 (s, 1H), 2.60 (s, 6H), 2.37 (s, 3H), 1.24 (s, 3H), 1.20 - 1.07 (m, 4H) C-25

480.0 (1.79) 8.51 - 8.22 (m, 2H), 8.11 (dd, J = 8.1, 2.0 Hz, 1H), 8.00 (dd, J = 11.0, 8.2 Hz, 1H), 7.51 (s, 1H), 3.70 (q, J=7.2 Hz, 2H), 3.17 (s, 1H), 1.15 (dt, J = 18.7, 7.2 Hz, 7H) C-26

494.0 (1.96) 8.42 - 8.39 (m, 1H), 8.38 (s, 1H), 8.12 (dd, J = 8.1, 2.0 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.51 (s, 1H), 4.27 (s, 3H), 3.69 (q, J = 7.3 Hz, 2H), 3.17 (s, 1H), 1.13 (m, 7H) C-27

497.0 (1.89) 9.18 (d, J = 2.0 Hz, 1H), 8.70 (d, J = 2.1 Hz, 1H), 8.28 (s, 1H), 7.52 (s, 1H), 4.06 (t, J = 7.3 Hz, 2H), 3.17 (s, 1H), 2.64 (s, 6H), 2.40 (s, 3H), 1.25 (q, J = 7.4, 6.2 Hz, 3H), 1.20 -0.99 (m, 4H)

B. Biological Examples

The activity of the compounds of formula (I) of the present invention could be demonstrated and evaluated in biological tests described in the following. If not otherwise specified, the test solutions are prepared as follows: The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: acteone. The test solution is prepared at the day of use. Test solutions are prepared in general at concentrations of 2500 ppm, 1415 ppm and 800 ppm (wt/vol).

Boll Weevil (Anthonomus Grandis)

For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 µl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at about 25 ± 1° C. and about 75 ± 5% relative humidity for 5 days. Egg and larval mortality was then visually assessed. In this test, compounds C-1, C-2, C-3, C-4, C-5 at 2500 ppm showed over 75% mortality in comparison with untreated controls. Compounds C-6, C-7, C-9, C-10, C-11, C-12, C-13, C-14, C-15, and C-16 at 800 ppm showed over 75% mortality in comparison with untreated controls.

Tobacco Budworm (Heliothis Virescens)

For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 µl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at about 28 ± 1° C. and about 80 ± 5% relative humidity for 5 days. Egg and larval mortality was then visually assessed. In this test, compound C-1, C-2, C-3, C-4, C-5 at 2500 ppm showed over 75% mortality in comparison with untreated controls. Compounds C-6, C-7, C-9, C-10, C-11, C-13, C-14, C-15, and C-16 at 800 ppm showed over 75% mortality in comparison with untreated controls.

Green Peach Aphid (Myzus Persicae)

For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 ± 1° C. and about 50 ± 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed. In this test, compound C-1, C-2, C-3, C-4, C-5 at 2500 ppm showed over 75 % mortality in comparison with untreated controls.. Compounds C-4, C-7, C-8, C-9, C-10, C-11, C-12, C-13, C-14, C-15, C-16, and C-23 at 800 ppm showed over 75% mortality in comparison with untreated controls.

Vetch Aphid (Megoura Viciae)

For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 µl, using a custom built micro atomizer, at two replications. After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 ± 1° C. and about 50 ± 5% relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed. In this test, compound C-1, C-3, C-4 at 2500 ppm showed over 75% mortality in comparison with untreated controls.

Greenhouse Whitefly (Trialeurodes Vaporarirorum)

For evaluating control of Greenhouse Whitefly (Trialeurodes vaporariorum) the test unit consisted of 96-well-microtiter plates containing a leaf disk of egg plant leaf disk with white fly eggs. The compounds or mixtures were formulated using a solution containing 75% water and 25% DMSO. Different concentrations of formulated were sprayed onto the insect diet at 2.5 µl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at 23 ± 1° C., 65 ± 5% RH for 6 days. Mortality of hatched crawlers was then visually assessed. In this test, compound C-4, C-5 at 2500 ppm showed over 75% mortality in comparison with untreated controls. Compounds C-4, C-6, C-11, C-13, C-15, and C-16 at 800 ppm showed over 75% mortality in comparison with untreated controls.

Yellow Fever Mosquito (Aedes Aegypti)

For evaluating control of yellow fever mosquito (Aedes aegypti) the test unit consisted of 96-well-microtiter plates containing 200 µl of tap water per well and 5-15 freshly hatched A. aegypti larvae. The active compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5 µl, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at 28 + 1° C., 80 + 5% RH for 2 days. Larval mortality was then visually assessed. In this test, compounds C-1, C-3, C-4, C-6, C-7, C-9, C-10, C-11, C-12, C-13,and C-14 at 800 ppm showed over 75% mortality in comparison with untreated controls.

Green Soldier Stink Bug (Nezara Viridula)

The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) distilled water: aceteone. Surfactant (Kinetic) is added at a rate of 0.01% (vol/vol).The test solution is prepared at the day of use. Soybean pods are placed in 90 × 50 mm glass Petri dishes lined with moistened filter paper and inoculated with ten late 3rd instar N. viridula. Using a hand atomizer, an approximately 2 ml solution is sprayed into each Petri dish. Treated set-up is kept at about 25-26° C. and relative humidity of about 65-70%. Percent mortality is recorded after 5 days. In this test, compounds C-1, C-3, C-4, C-5, C-6, C-7, C-9, C-10, C-11, C-14, C-15, and C-23 at 800 ppm showed over 75% mortality in comparison with untreated controls. 

1. A compound of formula (I)

wherein the rings A and B are fully unsaturated; Y is C=X, wherein X is O or S; E is N(R³) or C(R⁴); Q is N, N(R⁵) or C(R⁶); R¹ is H, halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy, C₁-C₆-sulfenyl, C₁-C₆-sulfinyl, or C₁-C₆-sulfonyl, which groups are unsubstituted or halogenated; R³, R⁵are independently C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which are unsubstituted or halogenated; C(=O)OR^(A), NR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C), C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C), C(=O)R^(D), C(=S)R^(D), SO₂NR^(B)R^(C), S(═O)_(m)R^(E); phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); R², R⁴, R⁶ are independently H, halogen, N₃, CN, NO₂, SCN, SF₅, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, tri-C₁-C₆-alkylsilyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkoxy, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxyx-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen, C(=O)OR^(A), NR^(B)R^(C), NOR^(A), ONR^(B)R^(C), C₁-C₆-alkylen-NR^(B)R^(C), O-C₁-C₆-alkylen-NR^(B)R^(C), C₁-C₆-alkylen-CN, NH-C₁-C₆-alkylen-NR^(B)R^(C), C(═O)NR^(B)R^(C), C(=O)R^(D), C(=S)R^(D), SO₂NR^(B)R^(C), S(═O)_(m)R^(E); phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); G is phenyl, or a 5- or 6-membered hetaryl; W is S, S(O), or S(O)₂; each R^(X) is independently —C(CN)R⁷R⁸, —C(R^(O))═N—N(R^(M)R^(N)), —C(R^(O))═N—O(R^(L)); C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹; or a group of formula (I.1)

wherein the ring L is a 5- or 6-membered saturated, partially or fully unsaturated carbo- or heterocycle; wherein the ring L is a saturated, partially or fully saturated carbo- or heterocycle, which carobo- or heterocycle is unsubstituted or substituted with one or more, same or different substituents R¹⁰, and wherin said heterocyclic ring contains one or more, same or different and wherein said heteroatoms O and N are oxidized or non-oxidized; wherein ring J is partially or fully unsaturated and unsubstituted or substituted with one or more, same or different substituents R¹¹; and wherein “&” means the connection to the remainder of the molecule at the position of R^(X) in formula (I); R⁷, R⁸ are independently H, halogen, CN, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylsulfanyl, C₁-C₄-alkylsulfanyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfinyl-C₁-C₄-alkyl, C₁-C₄-alkylsulfonyl-C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl; R⁹ halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, C(═O)OH, C(═O)NH₂, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl, C₁-C₄-alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino, di-(C₁-C₄)alkylcarbonylamino, C1-C₄-alkoxycarbonylamino, or a group —C(R⁹¹)═NOR⁹²; phenyl, which is unsubstituted or substituted with one or more, same or different substituents selected from halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl and C(=O)C₁-C₄-haloalkyl; C₁-C₄-alkyl which is unsubstituted or substituted with one or more, same or different substituents R⁹³; R⁹¹ and R⁹² are independently H, C₁-C₄-alkyl, or C₁-C₄-haloalkyl; R⁹³ is halogen, CN, NH₂, C(═O)H, OH, C₃-C₆-cycloalkyl, hydroxycarbonyl, aminocarbonyl, C₁-C₄-haloalkoxy, C₁-C₄-alkoxy, C₁-C₄-haloalkylsulfanyl, C₁-C₄-haloalkylsulfinyl, C₁-C₄-haloalkylsulfonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl, di-(C₁-C₄)alkylaminocarbonyl, C₁-C₄alkylaminocarbonyl, C₁-C₄-alkylcarbonylamino, di-(C₁-C₄)alkylcarbonylamino, C₁-C₄-alkoxycarbonylamino, a group —C(R⁹¹)═NOR⁹²; each R¹⁰, R¹¹ are independently H, halogen, CN, OH; C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, or C₁-C₄-alkoxy-C₁-C₄-alkyl, which groups are unsubstituted or halogenated; each R^(A) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents R^(F); each R^(B) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F); each R^(C) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkyl-carbonyl, or C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); each moiety NR^(B)R^(C) may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(=O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; each R^(D) is independently H, CN, OH, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₃-cycloalkyl, C₃-C₃-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); each R^(E) is independently C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which are unsubstituted or substituted with halogen; or phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); each R^(L) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with one or more, same or different substituents selected from halogen and CN; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substitutents R^(F); each R^(M) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, which groups are unsubstituted or substituted with one or more, same or different substituents R^(F); each R^(N) is independently H, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, C₁-C₆-alkyl-carbonyl, C₁-C₆-alkoxy-carbonyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); each moiety NR^(M)R^(N) may also form an N-bound, saturated 5- to 8-membered heterocycle, which in addition to the nitrogen atom may have 1 or 2 further heteroatoms or heteroatom moieties selected from O, S(=O)_(m) and N—R′, wherein R′ is H or C₁-C₆-alkyl and wherein the N-bound heterocycle is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; each R^(O) is independently H, CN, OH, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-cycloalkoxy-C₁-C₄-alkyl, which groups are unsubstituted or substituted with halogen; phenyl or benzyl, wherein the phenyl ring is unsubstituted or substituted with one or more, same or different substituents R^(F); each R^(F) is independently halogen, N₃, OH, CN, NO₂, SCN, SF₅, C₁-C₆ alkyl, C₁-C₆- alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₁-C₆-alkoxy-C₁-C₄ alkyl, C₁-C₆-alkoxy-C₁-C₄-alkoxy, C₃-C₆-cycloalkyl, C₃-C₆ cycloalkoxy, C₃-C₆-cycloalkyl-C₁-C₄ alkyl, C₃-C₆-cycloalkoxy-C₁-C₄ alkyl, which groups are unsubstituted or substituted with halogen; R^(W) is C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, which groups are halogenated or non-halogenated; benzyl, or phenyl, which is unsubstituted or substituted with R^(F); the index n is 0, 1, 2, 3, or 4 if G is phenyl or a 6-membered hetaryl; or 0, 1, 2, or 3 if G is a 5-membered hetaryl; and the index m is 0, 1 or 2; and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.
 2. The compound of formula (I) according to claim 1, wherein R¹ is H, C₁-C₃-alkyl, or C₁-C₃-alkoxy, which groups are unsubstituted or halogenated; R² is H, halogen, C₁-C₃-alkyl, C₁-C₃-alkoxy, C₂-C₃-alkenyl, or C₂-C₃-alkynyl, which groups are unsubstituted or halogenated.
 3. The compound of formula (I) according to claim 1, wherein the compound of formula (I) is a compound of formula (I.A), (I.B) or (I.C);

wherein all variables have a meaning as defined for formula (I).
 4. The compound of formula (I.A) according to claim 3, wherein R³ C₁-C₃-alkyl, C₃-C₆-cycloalkyl, C₃-C₆-cycloalkyl-C₁-C₂-alkyl, which groups are unsubstituted or halogenated; R⁶ is H, or C₁-C₃-alkyl or C₁-C₃-haloalkyl.
 5. The compound of formula (I.B) according to claim 3, wherein R⁴ is H, or C₁-C₃ alkyl, or C₁-C₃-haloalkyl; R⁵ is C₁-C₃-alkyl, or C₁-C₃-haloalkyl.
 6. The compound of formula (I) according to claim 1, wherein G is phenyl or pyridyl.
 7. The compound of formula (I) according to claim 1, wherein R^(W) is C₁-C₃-alkyl or C₁-C₃-haloalkyl.
 8. The compound of formula (I) according to claim 1, wherein each R^(X) is independently —C(CN)R⁷R⁸ or C₃-C₆-cycloalkyl, which is substituted with CN and which either does not have any further substituents, or which is further substituted with one or more, same or different substituents R⁹; R⁷, R⁸ are independently C₁-C₃-alkyl or C₁-C₃-haloalkyl; R⁹ is halogen, C₁-C₃-alkyl, or C₁-C₃-haloalkyl.
 9. The compound of formula (I) according to claim 1, wherein each R^(X) is independently —C(R^(O))═N—O(R^(L)) or —C(R^(O))═N—N(R^(M)R^(N)); wherein each R^(O) is independently H, CN, C₁-C₃-alkyl, or C₁-C₃-haloalkyl; each R^(L) is independently H; or C₁-C₃-alkyl, C₃-C₅-cycloalkyl, C₃-C₅-cycloalkyl-C₁-C₃-alkyl, which groups are unsubstituted or substituted with halogen or CN; each R^(M), R^(N) is independently H, C₁-C₃-alkyl, or C₁-C₃-haloalkyl; or a group of formula (1.1), wherein the ring J is a 5- membered heterocycle; wherein the ring L is 5- or 6-membered saturated carbocycle, which is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, and C₁-C₃-haloalkyl; and wherein ring J is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C₁-C₃-alkyl, and C₁-C₃-haloalkyl.
 10. A pesticidal mixture comprising the compound of formula (I), as defined in claim 1, and a further pesticidal ingredient.
 11. (canceled)
 12. A method for combating or controlling invertebrate pests, comprising contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound of the formula (I) according to claim 1 .
 13. A method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound of the formula (I), according to claim 1 .
 14. A seed comprising a compound of the formula (I), as defined in claim 1, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
 15. (canceled) 